Chromium compounds and uses thereof

ABSTRACT

Novel chromium-containing compounds, such as, for example, chromium pyrrolides, are prepared by forming a mixture of a chromium salt, a metal amide, and an electron pair donor solvent, such as, for example, an ether. These novel chromium-containing, or chromium pyrrolide, compounds can be used either unsupported or supported on an inorganic oxide support to trimerize and/or polymerize olefins.

This application is a divisional application of Ser. No. 07/698,515filed May 10, 1991, now U.S. Pat. No. 5,198,563, which is acontinuation-in-part of application Ser. No. 07/454,554, filed Dec. 21,1989, which is a continuation-in-part of application Ser. No.07/392,688, filed Aug. 10, 1989, both now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to chromium catalysts to trimerize and/orpolymerize olefins. This invention also relates to a process totrimerize and/or polymerize olefins.

Supported chromium oxide catalysts have been a dominant factor in theproduction of olefin polymers, such as polyethylene of copolymers ofethylene and hexane. These catalysts can be used in a variety ofpolymerization processes. However, most known chromium compounds must besupported to be catalytically active. Furthermore, most supportedchromium compounds are useful only for olefin polymerization. If anolefin copolymer is desired, the polymerization process becomes morecomplex in that two different monomers must be fed to the polymerizationreactor.

Olefin trimerization catalysts are also known in the art, but usuallylack selectivity to a desired product and also have a low product yield.However, olefin trimerization, if done efficiently, is a process toprovide useful olefins, which in turn, can be further trimerized or,optionally, incorporated into a polymerization process.

SUMMARY OF THE INVENTION

Therefore, it is an object of this invention to provide novel chromiumcompounds.

It is yet another object of this invention to provide a process toprepare at least one novel chromium compound.

It is a further object of this invention to provide an improved processto trimerize olefins.

It is yet another object of this invention to provide a process topolymerize olefins.

It is a further object of this invention to provide an improved olefintrimerization catalyst.

It is yet another object of this invention to provide an olefinpolymerization catalyst.

Therefore, in accordance with this invention, novel chromium-containingcompounds are prepared from a reaction mixture comprising a chromiumsalt, a metal amide, and any electron pair donor solvent, such as, forexample, an ether.

In accordance with another embodiment of this invention thischromium-containing compound can be used, either supported orunsupported, to trimerize or polymerize olefins.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a computer generated ball and stick projection, with theexception of the chromium atoms which are represented as thermalellipsoids, or a simplified structural representation or formula, of amolecule of Product I, Cr₅ (NC₄ H₄)₁₀ (OC₄ H₈)₄, as determined by singlecrystal x-ray crystallography, and

FIG. 2 is a further simplified ball and stick projection, with theexception of the chromium atoms which are represented as thermalellipsoids, or a structural representation, of the same molecule shownin FIG. 1.

FIG. 3 is a computer generated ORTEP drawing of the structure, or asimplified structural representation or formula, of a molecule ofProduct III, [Cr(NC₄ H₄)₄ ]⁻², as determined by single crystal x-raycrystallography.

FIG. 4 is a further simplified ball and stick projection, with theexception of the chromium atoms which are represented as thermalellipsoids, or a structural representation, of the same molecule shownin FIG. 3, however, the entire crystal structure or lattice, with theformula Cr(NC₄ H₄)₄ Na₂.20C₄ H₈ is shown.

FIG. 5 is a computer generated ORTEP drawing of the structure, or asimplified structural representation or formula, of a molecule ofProduct IV, [Cr(NC₄ H₄)₅ (OC₄ H₈)]⁻², as determined by single crystalx-ray crystallography, and

FIG. 6 is a further simplified ball and stick projection, with theexception of the chromium atoms which are represented as thermalellipsoids, or a structural representation, of the same molecule shownin FIG. 5, however the entire crystal structure or lattice, with theformula [Cr(NC₄ H₄)₅ (OC₄ H₈)][Na]₂.4(OC₄ H₈), is shown.

FIG. 7 is a computer generated ORTEP drawing of a molecule of Product V,Cr(NC₄ H₄)₃ Cl(O₂ C₂ H₄ (CH₃)₂)₃ Na, which includes the entire crystalstructure or lattice, as determined by single crystal x-raycrystallography.

FIG. 8 is a further simplified ball and stick projection of the samemolecule shown in FIG. 7.

FIG. 9 is a further simplified ball and stick projection of [Cr(NC₄ H₄)₃Cl(O₂ C₂ H₄ (CH₃)₂)]⁻¹, with the exception of the chromium atom which isrepresented as a thermal ellipsoid. This is the same molecule as thatshown in FIGS. 7 and 8, however, the entire crystal structure, orlattice, is not shown in FIG. 9.

DETAILED DESCRIPTION OF THE INVENTION The Chromium Compounds

The inventive chromium compounds, which can be used preferably forolefin trimerization and, optionally, olefin polymerization, can beproduced by forming a reaction mixture comprising a chromium salt, ametal amide, and any electron pair donor solvent, such as, for example,an ether. As used in this disclosure, the inventive chromium compoundsare referred to by a variety of interchangeable names, such as inventiveor novel chromium compound(s), chromium complex(es), chromium pyrrolecomplex(es) and/or chromium pyrrolide.

The chromium salt can be one or more organic or inorganic chromiumsalts, wherein the chromium oxidation state is from 0 to 6. As used inthis disclosure, chromium metal is included in this definition of achromium salt. Generally, the chromium salt will have a formula ofCrX_(n), wherein X can be the same or different and can be any organicor inorganicradical, and n is an integer from 1 to 6. Exemplary organicradicals can have from about 1 to about 20 carbon atoms, and areselected from the group consisting of alkoxy, ester, ketone, and/oramido radicals. The organic radicals can be straight-chained orbranched, cyclic or acyclic, aromatic or aliphatic, and can be made ofmixed aliphatic, aromatic, and/or cycloaliphatic groups. Exemplaryinorganic radicals include, but are not limited to halides, sulfates,and/or oxides.

Preferably, the chromium salt is a halide, such as, for example chromousbromide, chromic bromide, chromous iodide, chromic iodide, chromousfluoride, chromic fluoride, chromous chloride, chromic chloride, andmixtures thereof. Most preferably, the chromium salt is a chloride, suchas, for example chromous chloride and/or chromic chloride, due to simpleseparation of the reaction by-products such as, for example, sodiumchloride, as well as relatively low cost.

The metal amide can be any metal amide that will react with a chromiumsaltto form a chromium-amido complex. Broadly, the metal amide can beany heteroleptic or homoleptic metal complex or salt, wherein the amideradical can be any nitrogen-containing organic radical. The metal amidecan be either affirmatively added to the reaction, or generated in-situ.Generally, the metal amide will have from about 1 to about 20 carbonatoms. Exemplary metal amides include, but are not limited to, primaryand/or secondary amines, any alkali metal (Group IA, and includinghydrogen, of the Periodic Table) amide and/or any alkaline earth metal(Group IIA of the Periodic Table) amide. The hydrocarbyl portion of thesalt of the metal amide is selected from the group consisting ofstraight chain or branched, cyclic or acyclic, aromatic or aliphatic,and mixtures of two or more thereof. Preferably, the metal amide isselected from a Group IA, and including hydrogen, or Group IIA metalamide, due to ease ofreaction with chromium halides.

Exemplary preferred metal amides include, but are not limited to,lithium dimethylamide, lithium diethylamide, lithium diisopropylamide,lithium dicyclohexylamide, sodium bis(trimethylsilyl)amide, sodiumindolide, sodium pyrrolide, and mixtures of two or more thereof. Mostpreferably, the metal amide is a pyrrolide. As used in this disclosure,a pyrrolide isdefined as a compound comprising a 5-membered,nitrogen-containing heterocycle, such as, for example, pyrrole,derivatives of pyrrole, and mixtures thereof. Exemplary pyrrolides areselected from the group consisting of hydrogen pyrrolide (pyrrole),lithium pyrrolide, sodium pyrrolide, potassium pyrrolide, cesiumpyrrolide, and/or the salts of substituted pyrrolides, because of highreactivity and activity with the other reactants. Examples of salts ofsubstituted pyrrolides include, but are not limited to sodium2,5-dimethyl pyrrolide and/or 3,4-dimethyl pyrrolide. When the metalamide is a pyrrolide ligand, the resultant chromium compound is achromium pyrrolide.

The electron pair donor solvent can be any electron pair donor solventto affect a reaction between the chromium salt and the metal amide.While notwishing to be bound by theory, it is believed that the electronpair donor solvent can be a reaction solvent, as well as a possiblereactant. Exemplary electron pair donor solvents include, but are notlimited to, nitrogen-, oxygen-, phosphorous-, and/or sulfur-containingcompounds and/or ethers.

Exemplary nitrogen-containing compounds include, but are not limited tonitriles, such as, for example, acetonitrile; amines, such as, forexample, pyridine, and/or amides. Additional exemplarynitrogen-containingcompounds include, but are not limited to,nitromethane, dimethylpyridine, dimethylformamide, N-methylformamide,aniline, nitrobenzene, tetramethyldiaminomethane, hexamethyldisilazane,and/or pyrrolidone.

Exemplary oxygen-containing compounds include, but are not limited to,acetone, ethyl acetate, methyl acetate, methanol, ethanol, ethyl methylketone, acetaldehyde, furan, and/or hexamethyldisiloxane.

Exemplary phosphorous-containing compounds include, but are not limitedto,hexamethylphosphoramide, hexamethylphosphorous triamide,triethylphosphite,tributylphosphine oxide, and/or triethylphosphine.

Exemplary sulfur-containing compounds include, but are not limited to,carbon disulfide, dimethylsulfoxide, tetramethylene sulfone, triophene,and/or dimethylsulfide or mixtures thereof.

The ether in the reaction mixture can be one or more ether compounds toaffect a reaction between the chromium salt and the metal amide. Whilenotwishing to be bound by theory, it is believed that the ether can be areaction solvent, as well as a possible reactant. The ether can be anyaliphatic and/or aromatic compound containing an R--O--R functionality,wherein the R groups can be the same or different, but preferably is nothydrogen. Preferred ethers are aliphatic ethers, for safety reasons inthat aromatic ethers are human toxins. Furthermore, the preferred ethersare those which facilitate a reaction between a chromium halide and aGroup IA or Group IIA metal pyrrolide, and also can be easily removedfromthe reaction mixture. Exemplary compounds include, but are notlimited to, tetrahydrofuran, dioxane, diethylether, dimethoxyethane(glyme), diglyme, triglyme, and mixtures of two or more dimethoxyethane(glyme), diglyme, triglyme, and mixtures of two or more thereof. Mostpreferably, the ether is selected from the group consisting oftetrahydrofuran, derivatives of tetrahydrofuran, dimethoxyethane,derivatives of dimethoxyethane, and mixtures thereof, for the reasonsgiven above, as well as the reason that the preferred salt of an amineis soluble in these ethers.

The amount of each reactant used to prepare one or more of the novelchromium compounds can vary, based on the desired chromium compoundproduct. Any amount of each reactant can be used to produce the novelchromium compounds, depending on the desired product. Different reactionstoichiometries can produce different chromium compounds. For example,thereaction of about one mole of chromium (II) with about two moles ofsodium pyrrolide can produce different products than reacting about onemole of chromium (II) with an excess of sodium pyrrolide. Furthermore,as stated earlier, selection of different, although similar reactants,can produce different products. For example, using eithertetrahydrofuran or dimethoxyethane can result in a different reactionproduct.

The three reactants can be combined in any manner under conditionssuitableto form a solution comprising one or more of the inventivechromium compounds. The reaction preferably occurs in the absence ofoxygen and therefore under an inert, such as, for example, nitrogenand/or argon. Thereaction pressure can be any pressure sufficient tomaintain the reactants in a liquid state. Generally, pressure within therange of from about atmospheric pressure to about three atmospheres areacceptable. For ease of operation atmospheric pressure is generallyemployed.

The reaction temperature can be any temperature which maintains theether in a liquid form. In order to effectuate a more efficientreaction, temperatures near the boiling point of the ether arepreferred. Most preferably, the reaction temperature is at the boilingpoint of the ether and the reaction mixture is refluxed for a period oftime.

The reaction time can be any amount of time necessary for the reactionto occur. Depending on the reactants, as well as the reactiontemperature andpressure, reaction time can vary from about 1 minute toabout 1 week. Usually, reaction time ranges from about 3 hours to about5 days. Under optimum conditions, the reaction time can be within therange of from about 3 to about 48 hours.

After the reaction is complete, a solid reaction product can berecovered by any method known in the art. Preferably, though notrequired, upon completion of the reaction, the reaction mixture first isfiltered to remove any reaction insoluble by-products such as, forexample, salts, like sodium chloride, prior to any other treatment.Although removal of any reaction by-products is not necessary, suchremoval preferably is donein order to expedite later purification of thechromium product. After filtering, one exemplary method to recover asolid reaction product is to remove the excess ether from the reactionmixture. The excess electron pair donor solvent, such as, for example anether, can be removed according to any method known in the art.Exemplary electron pair donor solvent, such as, for example an ether,removal methods include, but are not limited to, slow evaporation, undervacuum and/or a nitrogen purge.

Other electron pair donor solvent, such as, for example an ether,removal procedures can be used either alone or in combination. Forexample, the reaction mixture can be filtered and then vacuum dried.Preferably, the reaction mixture is heated slowly and maintained attemperature within therange of about 10° C. to about 300° C., preferablyabout 25° C. to about 200° C., under a vacuum, for safety, to remove theexcess electron pair donor solvent, such as, for example an ether. Theresultant solid reaction product is one or more of the inventivechromium compounds.

Alternatively, the reaction mixture can be filtered to remove any solidreaction by-product solids and the filtered reaction mixture can becontacted with a non-polar organic solvent. Addition of a non-polarorganic solvent causes one or more of the inventive chromium compoundsto form a solid precipitate. Exemplary non-polar organic solventinclude, butare not limited to, pentane, hexane, cyclohexane, heptane,and mixtures thereof. Most preferably pentane is added to the filteredreaction mixturebecause of the availability and ease of use.

The precipitated inventive chromium compounds can be recovered by anymethod known in the art. The simplest procedure to recover the inventiveprecipitated chromium compounds is by filtration.

The reaction mixture and the resultant solid reaction products, asstated earlier, are kept in an oxygen-free atmosphere at all times.Preferably, due to availability and ease of use, an inert atmospheresuch as, for example, nitrogen, is the ambient.

Numerous chromium compounds can be prepared in accordance to theinvention,by varying the reactants and/or the quantity of each reactantemployed. Therecovered, novel chromium compound or compounds can be usedfor olefin trimerization and/or polymerization without furtherpurification.

Optionally, the chromium compound can be purified in accordance with anymethod known in the art. For example, one of the simplest purificationprocedures is to wash the recovered solid with a non-polar organicsolventsuch as, for example, toluene. Preferably, a non-polar aliphaticorganic solvent is used for best results. Exemplary wash solventsinclude, but arenot limited to, pentane, hexane, cyclohexane, heptane,and mixtures thereof. Most preferably, pentane is the wash solvent.

The inventive chromium compounds can be used as a supported and/orunsupported catalyst for olefin trimerization and/or polymerization. Asupported chromium catalyst can be prepared according to any methodknown in the art. Any support useful to support chromium catalyst can beused. Exemplary catalyst supports include, but are not limited to,inorganic oxides, either alone or in combination, phosphated inorganicoxides, and mixtures thereof. Particularly preferred are supportsselected from the group consisting of silica, silica-alumina, alumina,fluorided alumina, silated alumina, thoria, aluminophosphate, aluminumphosphate, phosphated silica, phosphated alumina, silica-titania,coprecipitated silica/titania,and mixtures, thereof, fluorided/silatedalumina, being presently preferred, as well as any one or more of thesesupports which can contain chromium. The presently most preferredcatalyst support is because of the greatest trimerization activity, isaluminophosphate, as disclosed in U.S.Pat. No. 4,364,855 (1982), hereinincorporated by reference.

The supported chromium catalyst system can be prepared according to anymethod known in the art. For example, the reaction mixture, whichpreferably has been filtered to remove any particulate reactionby-products and contains one or more of the novel chromium pyrrolidecompounds, is combined and thoroughly contacted with a catalyst support.Excess electron pair donor solvent, such as, for example an ether, doesnot have to be removed prior to contacting the catalyst support.However, a solid chromium pyrrolide compound can be re-dissolved in anelectron pair donor solvent, such as, for example an ether, if desired.The chromium pyrrolide/ether solution is usually a blue or blue/greencolor, although other colors can be observed.

The catalyst support usually is insoluble in the ether/chromiumpyrrolide complex solution. Any excess of the chromium pyrrolide inrelation to the catalyst support is sufficient. However, usually, atleast about 5 grams of chromium pyrrolide compound per gram of catalystsupport is sufficient.Preferably about 0.001 to about 1 grams ofchromium pyrrolide compound per gram of support, and most preferablyabout 0.01 to about 0.5 grams of chromium pyrrolide compound per gram ofsupport is used for best support loading and most efficient use of thereagents. This mixture can be contacted and mixed at any time,temperature, and pressure to thoroughly contact the chromium pyrrolidecompound and support. For ease of use, ambient temperatures andpressures are preferred. Mixing times can be up to about 24 hours,preferably about 5 seconds to about 10 hours, and most preferably about5 seconds to about 8 hours. Longer times usually provide no additionalbenefit and shorter times can be insufficient for thorough contacting.

After the support is added and thoroughly combined with the chromiumpyrrolide it is collected by filtration, vacuum dried, then anactivating compound, usually as a solution of one or more Lewis acidsand/or metal alkyls, preferably in a hydrocarbon solvent, is added tothe support/chromium pyrrolide mixture. As used in this disclosure, aLewis acid is defined as any compound that is an electron acceptor.Preferably, the activating compound is a compound that can be consideredboth a Lewis acid end a metal alkyl. Preferred activating compoundswhich are both a metal alkyl and a Lewis acid include, but are notlimited to, alkylaluminum compounds, and mixtures thereof. The mostpreferred alkylaluminum compound is triethylaluminum, for best resultsin catalyst activity.

The hydrocarbon solvent can be any hydrocarbon that will dissolve theLewisacid. Preferred hydrocarbons include, but are not limited to,aromatic compounds having from about 6 to about 50 carbon atoms permolecule. Most preferably, the hydrocarbon solvent is toluene, for easeof removal and minimal interference with the resultant catalyst.

Any amount of activating compounds, such as a metal alkyl and/or a Lewisacid is sufficient to activate and/or react with the chromium pyrrolidecatalyst. Usually about 200 grams of Lewis acid per gram of chromium canbe used. Preferably, about 1 to about 100 grams of activating compound,such as a metal alkyl and/or a Lewis acid per gram of chromiumpyrrolide, and most preferably about 5 to about 30 grams of activatingcompound, suchas a metal alkyl and/or a Lewis acid per gram of chromiumpyrrolide are used, for best catalyst activity. However, the amount ofLewis acid employed can vary with the catalyst support used. Forexample, if the support is silica and/or alumina, too much activatingcompound, such as a metal alkyl and/or a Lewis acid can decreasecatalyst activity. However, asimilar amount of activating compound, suchas a metal alkyl and/or a Lewisacid used with an aluminophosphatesupport does not always significantly decrease catalyst activity.

As disclosed earlier, the mixture of chromium pyrrolide, catalystsupport, and activating compound, such as a metal alkyl and/or a Lewisacid are mixed and/or contacted under a dry, inert atmosphere at alltimes. Any pressure can be used during the contacting; for ease of use,atmospheric pressure is preferred. Any temperature can be used duringthe contacting; for ease of use, room temperature, or ambienttemperature, is preferred. Some care should be taken during the mixing,so as not to destroy the physical integrity of the chromium pyrrolide,catalyst support, and resultant supported catalyst. The three-componentmixture can be contactedfor any amount of time sufficient to prepare andactivate a chromium catalyst. Usually times in the the range of aboutone minute to about one week are sufficient. Preferably, times in therange of about 30 minutes toabout 24 hours are used, and most preferablytimes in the range of about one hour to about 12 hours are used. Tooshort of mixing times can result in incomplete contacting and too longof mixing times will not provide anyadditional catalytic benefit.

An alternative, and presently preferred, method to produce a supportedcatalyst is to combine one or more solid, inventive chromium pyrrolidecompounds with a hydrocarbon solvent, a disclosed earlier, such as, forexample, toluene, and an activating compound, such as a metal alkyland/ora Lewis acid, as disclosed earlier, such as, for example,triethylaluminum.This mixture can be stirred for any time sufficient todissolve the chromium pyrrolide compound, at any pressure ortemperature. Usually, times of about one minute to about one week,preferably about one hour to about 24 hours, and most preferably withinthe range of about three hours to about 12 hours are used. For ease ofoperation, ambient temperatures and pressures are used. Usually, a brownsolution will result.

After the solution is sufficiently mixed, a support is added to thesolution and stirred to thoroughly contact the solution and support. Thequantity of support is any amount sufficient to support the chromiumpyrrolide compound. Generally, the amount of support necessary is thesameas that disclosed in the previous ememplary process. Any suitablepressure and temperature can be used, although ambient temperature andpressure arepreferred for ease of use. Usually, the mixing and/orcontacting time is within the range of about 30 minutes to about oneweek, preferably from about 3 hours to about 48 hours. Most preferably,the mixing and/or contacting time is within the range of about 5 hoursto about 24 hours, tomaximize efficiency and result in a thoroughlycontacted support.

The solution then can be filtered to recover a solid catalytic product.Thecatalytic product, as with the reactants and reactions, is preferablykept under an inert atmosphere to maintain chemical stability.

If the chromium compound, such as, for example, a chromium pyrrolide, isrecovered and is to be used as an unsupported trimerization and/orpolymerization catalyst, olefins can be trimerized or polymerized in apresence of one or more of the inventive homogeneous chromium compounds,asaturated hydrocarbon as a diluent, and Lewis acid. Optionally,hydrogen can be added to the reactor to accelerate the reaction.

Reactants

Reactants applicable for use in polymerization with the catalyst andprocesses of this invention are olefinic compounds which can polymerize,i.e., react the same or with other olefinic compounds. Catalyst of theinvention can be used to polymerize at least one linear or branchedmono-1-olefin having about 2 to about 8 carbon atoms. Exemplarycompounds include, but are not limited to, ethylene, propylene,1-butene, 1-pentene,1-hexene, 1-octene, and mixtures thereof.

Reactants applicable for use in the trimerization process, i.e., thecombination of any three olefins, of this invention are olefiniccompoundswhich can a) self-react, i.e., trimerize, to give usefulproducts such as, for example, the self reaction of ethylene can giveone hexene; and/or b) olefinic compounds which can react with otherolefinic compounds, i.e., co-trimerize, to give useful products such as,for example, co-trimerization of ethylene plus hexane can give onedecene and/or 1-tetradecene, co-trimerization of ethylene and 1-butenegives one octene,or 1-decene and ethylene can give 1-tetradecene and/or1-docosene. As used herein, the term "trimerization" is intended toinclude "co-trimerization"as defined above.

Suitable trimerizable olefinic compounds are those compounds having fromabout 2 to about 30 carbon atoms per molecule and having at least oneolefinic double bond. Exemplary compounds include, but are not limitedto acyclic and cyclic olefins such as, for example, ethylene, propylene,1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 1-hexene,2-hexene,3-hexene, 1-heptene, 2-heptene, 3-heptene, the four normaloctenes, the four normal nonenes, and mixtures of any two or morethereof. If branched and/or cyclic olefins are used as reactants, whilenot wishing to be boundby theory, it is believed that steric hindrancecould hinder the trimerization process. Therefore, the branched and/orcyclic portion(s) ofthe olefin should be distant from the carbon-carbondouble bond.

The reaction products, i.e., trimers and/or polymers, can be preparedfrom the catalyst systems of this invention by solution reactions,slurry reactions, and/or gas phased reaction techniques usingconventional equipment and contacting processes. Contacting of themonomer or monomers with the catalyst system can be effected by anymanner known in the art ofsolid catalyst. One convenient method is tosuspend the catalyst system in an organic medium and to agitate themixture to maintain the catalyst system in suspension throughout thetrimerization and/or polymerization process. Other known contactingmethods such as fluidized bed, gravitatingbed, and fixed bed can also beemployed. Optionally, hydrogen can be added to the reactor to acceleratethe reaction.

The catalyst systems of this invention are particularly suitable for useinslurry trimerization and/or polymerizations. The slurry process isgenerally carried out in an inert diluent (medium), such as a paraffin,cycloparaffin, or aromatic hydrocarbon. One exemplary reactor diluent isisobutane. When the reactant is predominately ethylene, a temperature inthe range of about 60° to about 110° C. is employed.

Products

The olefinic and/or polymeric products of this invention haveestablished utility in a wide variety of applications such as, forexample, as monomers for use in the preparation of homopolymers,copolymers, and/or terpolymers. The polymeric products of this inventionhave established utility in a wide variety of applications such as forexample, polyethylene.

The further understanding of the present invention and its advantageswill be provided by reference to the following examples.

EXAMPLES Preparation of Chromium-Containing Compounds

Manipulations of all reactants were carried out either in a dryboxemploying nitrogen, or in airless glassware employing vacuum ornitrogen. Tetrahydrofuran (THF), toluene, benzene, diethylbenzene(Aldrich, 97% mixture of 1,2-, 1,3-, 1,4- isomers) and pentane werepurified by distillation over sodiumbenzophenone ketyl under nitrogen,then degassed via a nitrogen purge. Dimethoxyethane (DME) (Aldrich,anhydrous) was degassed via nitrogen purge and used without furtherpurification. Pyrrole(Aldrich, 98%) was vacuum distilled over sodium,then degassed via nitrogenpurge. 2,5-Dimethylpyrrole was dried withcalcium sulfate and vacuum distilled. Sodium 2,5-dimethylpyrrolide (NaC₆H₈ N) was preparedby reacting 2,5-dimethylpyrrole with an excess ofsodium (40% by weight dispersion in mineral spirits) in refluxingtetrahydrofuran under nitrogen. Sodium pyrrolide was prepared byreacting pyrrole with an equivalent molar amount (1:1) of NaH (Aldrich,60% by weight in mineral oil) or sodium (40% dispersion by weight inmineral spirits) in dimethoxyethane or tetrahydrofuran (THF) at ambienttemperature under nitrogen. Triethylaluminum (TEA) (Aldrich 1.0M,hexanes and 1.9M toluene) was used as received. Ketjen Grade B alumina(Al₂ O₃) and Davison 952 silica (SiO₂) were the commercial materialsused as supports for catalyst preparations. Fluorided-alumina (F/Al₂O₃,15 wt % F) was prepared by the addition of a solution of NH₄ HF₂ inmethanol to Ketjen Grade B alumina. Phosphated silica (P/SiO₂, P/Simolar ratio=0.1) was prepared by the addition of a 10% H₃ PO₄ /Methanolsolution to Davison 952 silica. The aluminophosphate (AlPO₄) used in thefollowing experiments was made as described in McDaniel et al, U.S. Pat.No. 4,364,855 (1982). The supports were activated by placing up to 25 ginto a fritted quartz tube, fluidizing with air and calcining at 700°C., except for P/SiO₂ at 350° C., for 3 hours. The air stream wasswitched to nitrogen until the support cooled to ambient temperature.

Chromium pyrrolide complexes were typically prepared from anhydrouschromium (II or III) chloride and sodium pyrrolide as follows:

A typical synthetic procedure useful to prepare chromium pyrrolidecomplexes was that of reacting the chromium chlorides with sodiumpyrrolide (NaC₄ H₄ N, also referred to as NaPy) in refluxingtetrahydrofuran (THF). A molar reactant stoichiometry of 1CrCl₂ and2NaPy resulted in the isolation of a polymeric material, Product II, asthe major product and a pentanuclear complex, Product I, (Cr₅ (NC₄ H₄)₁₀(OC₄ H₈)₄), as the minor product,see Equation 1. Using molar excess ofNaPy resulted in the isolation of thedianionic square planar complex{Cr(NC₄ H₄)₄ }{Na}₂.2OC₄ H₈, Product III, and the octahedral complex{Cr(C₄ H₄ N)₅ (OC₄ H₈)}{Na}₂.40C₄ H₈, Product IV, see Equation 2. Eachof the products was isolated through precipitation, Product II, orcrystallization, Products I, III, IV, from THF solutions by the additionof pentane. ##STR1##

EXAMPLE I

To prepare the pentanuclear complex, Product I, (Cr₅ (NC₄ H₄)₁₀ (OC₄H₈)₄), and the polymeric material, Product II, chromous chloride (2.0g/16.27 mmole) was combined with sodiumpyrrolide (33.68 mmole) intetrahydrofuran and refluxed 20 hours. The reaction mixture was filtered(medium porosity frit) and the filtrate was used for fractionalcrystallization of both (Cr₅ (NC₄ H₄)₁₀ (OC₄ H₈)₄), Product I, and thepolymeric material, Product II, through the addition of pentane. Thepolymeric material crystallized as a blue solid followed by (Cr₅ (NC₄H₄)₁₀ (OC₄ H₈)₄) as opaque dark blue/purple crystals.

Analysis calculated for C₅₆ H₇₂ N₁₀ Cr₅, Product I: C, 55.62; H, 6.00;N, 11.58%, by weight. Found: C, 55.46; H, 6.32; N, 11.15%,by weight.Analysis found for Product II: Cr, 11.5; C, 59.75; H, 7.61; N, 9.17%, byweight, but variable upon precipitation conditions. An x-ray crystalstructure of Product I showed a pentanuclear complexincorporatingbridging amido-pyrrolyl, terminal amido-pyrrolyl, andtetrahydrofuran ligands (FIGS. 1 and 2).

EXAMPLE II

To prepare {Cr(NC₄ H₄)₄ }{Na}₂.20C₄ H₈, Product III, and {Cr(C₄ H₄ N)₅(OC₄ H₈)}{Na}₂.40C₄ H₈, Product IV, chromous chloride (3.0 g/24.4 mmole)was combined with sodium pyrrolide (100.9 mmole) in tetrahydrofuran andrefluxed 2 hours, see Equation 2. The reaction mixturewas filtered(medium porosity frit) and the filtrate was used for fractionalcrystallization of both {Cr(NC₄ H₄)₄ }{Na}₂.20C₄ H₈, Product III, and{Cr(C₄ H₄ N)₅ (OC₄ H₈)}{Na}₂.40C₄ H₈, Product IV, through the additionof pentane. Product III crystallized as translucent orange/red crystalsfollowed by Product IV as translucent purple crystals.While not wishingto be bound by theory, the formation of Product IV is believed to resultfrom the presence of chromic chloride in the chromous chloride reagent(Alfa, chromium (II) chloride, anhydrous, contains 5-10% by weightCrCl₃) used in the preparation.

Analysis calculated for C₂₄ H₃₂ N₄ O₂ CrNa₂, Product III: C, 56.94; H,6.32; N, 11.07% by weight. Found: C, 57.04; H, 6.30; N, 10.92%, byweight. Analysis calculated for C₄₀ H₆₀ N₅ O₅ CrNa₂, Product IV: C,60.90; 11, 7.67; N, 8.88% by weight. Found: C, 60.81; H, 7.74; N, 9.44%,by weight. An x-ray crystal structure of Product III showed a squareplanar complex incorporating terminal amido-pyrrolyl ligands (FIG. 4).An x-ray crystal structure of Product IV showed an octahedral complexincorporating terminal amido-pyrrolyl and a tetrahydrofuran ligand(FIGS. 5 and 6).

EXAMPLE III

The reaction product obtained from sodium pyrrolide and CrCl₃ was themost preferred in the preparation of an active catalyst. Pyrrole (7.0ml/100.9 mmole) was mixed with NaH (4.2 g of 60%, about 105 mmole) indimethoxyethane at ambient temperature until bubbling ceased. Chromicchloride (5.33 g/33.7 mmole) was added to the solution at ambienttemperature. The reaction mixture was refluxed under nitrogen for fivehours, see Equation 3. This resulted in a dark green solution. Thesolution was filtered (medium porosity frit) and stripped of solventundervacuum and pumped dry under vacuum for 12 hours. The resultantchromium pyrrolide complex was a green solid, Product V. It was used inthe preparation of an active catalyst without further purification.##STR2##

EXAMPLE IV

All single crystal x-ray structure analyses were performed byCrystalytics Company, Lincoln, Nebr. Examples IV, V, VI, and IX containthe resultant analytical and subsequently computer-generated data.

A single crystal x-ray structure was obtained for [Cr₅ (NC₄ H₄)₁₀ (OC₄_(H) ₈)₄ ], Product I, and shown in FIGS. 1 and 2. The description ofthe single-crystal sample, and amountingused for data collection are asfollows:

Color: Dark blue

Shape: Rectangular parallelepiped

Dimensions: 0.20×0.48×0.80 mm

Crystal Mount: Crystal was sealed inside a thin-walled glass capillarywithepoxy under N₂.

Crystal Orientation: Crystal was oriented with its longest edge nearlyparallel to the phi axis of the diffractometer.

Width at half-height from ω Scans: 0.38°

The space group and cell data are as follows:

Crystal System: Triclinic

Space Group and Number:² P⁻¹ -C_(i) ¹ (No. 2)

Number of Computer-Centered Reflections Used in the Least-SquaresRefinement of the Cell Dimensions: ##EQU1##Lattice Constants with esd's:

    ______________________________________                                        a = 10.803(2)Å                                                                          α = 85.59(2)°                                                                 V = 1407.9(6)Å.sup.3                           b = 9.825(2)Å                                                                           β = 96.23(2)°                                                                  Z = 1                                              c = 14.212(4)Å                                                                          δ = 109.99(2)°                                                                λ = 0.71073Å                            ______________________________________                                    

Molecular Weight: 1209.24 amu

Calculated Density: 1.427 g/cm⁻¹

Linear Absorption Coefficient:^(3a) 0.96 mm⁻¹

Tables I-V list the resultant parameters used to generate the molecularstructures shown in FIGS. 1 and 2.

                  TABLE I                                                         ______________________________________                                        Atomic Coordinates for Nonhydrogen Atoms in Crystalline                       [Cr.sub.s (NC.sub.4 H.sub.4).sub.10 (OC.sub.4 H.sub.8).sub.4 ].sup.a                                     Equivalent Isotropic                               Atom  Fractional Coordinates                                                                             Thermal Parameter                                  Type.sup.b                                                                          10.sup.4 x                                                                             10.sup.4 y                                                                              10.sup.4 z                                                                            B, Å.sup.2 × 10.sup.c              ______________________________________                                        Cr.sub.1                                                                            0.sup.d  0.sup.d   0.sup.d 25(1)                                        Cr.sub.2                                                                            636(1)   2281(1)   1500(1) 24(1)                                        Cr.sub.3                                                                            -1179(1) 841(1)    3122(1) 28(1)                                        N.sub.1a                                                                            -1155(3) 935(3)    715(2)  25(1)                                        C.sub.1a                                                                            -2195(4) 64(4)     1231(3) 31(1)                                        C.sub.2a                                                                            -3313(4) 390(5)    965(3)  41(1)                                        C.sub.3a                                                                            -3014(4) 1486(5)   257(3)  43(1)                                        C.sub.4a                                                                            -1728(4) 1791(4)   116(3)  34(1)                                        N.sub.1b                                                                            1566(3)  1902(3)   331(2)  29(1)                                        C.sub.1b                                                                            1753(4)  3095(4)   -306(3) 36(1)                                        C.sub.2b                                                                            3035(5)  3751(5)   -432(3) 51(2)                                        C.sub.3b                                                                            3736(4)  2986(5)   131(3)  51(2)                                        C.sub.4b                                                                            2823(4)  1865(4)   587(3)  38(1)                                        N.sub.1c                                                                            -320(3)  2997(3)   2480(2) 27(2)                                        C.sub.1c                                                                            375(4)   3732(4)   3273(3) 34(1)                                        C.sub.2c                                                                            29(5)    4919(4)   3383(3) 43(1)                                        C.sub.3c                                                                            -908(5)  4967(4)   2631(3) 42(1)                                        C.sub.4c                                                                            -1105(4) 3809(4)   2101(3) 32(1)                                        N.sub.1d                                                                            443(3)   350(3)    2743(2) 28(1)                                        C.sub.1d                                                                            1600(4)  715(4)    3289(3) 36(1)                                        C.sub.2d                                                                            2321(4)  -133(5)   3102(3) 46(2)                                        C.sub.3d                                                                            1567(5)  -1070(5)  2403(3) 46(2)                                        C.sub.4d                                                                            422(4)   -763(4)   2203(3) 36(1)                                        N.sub.1e                                                                            -1972(3) -1122(3)  3801(2) 35(1)                                        C.sub.1e                                                                            -1344(5) -2107(4)  4069(3) 41(1)                                        C.sub.2e                                                                            -2189(5) -3307(4)  4503(3) 44(1)                                        C.sub.3e                                                                            -3361(5) -3061(4)  4531(3) 47(1)                                        C.sub.4e                                                                            -3206(5) -1731(40  4097(3) 47(1)                                        O.sub.1f                                                                            2351(3)  3985(3)   1883(2) 32(1)                                        C.sub.1f                                                                            3536(4)  4018(4)   2483(3) 43(1)                                        C.sub.2f                                                                            4470(6)  5479(6)   2336(5) 76(2)                                        C.sub.3f                                                                            3642(5)  6408(5)   2147(4) 62(2)                                        C.sub.4f                                                                            2396(4)  5463(4)   1635(3) 40(1)                                        O.sub.1g                                                                            -2551(3) 1543(3)   3659(2) 35(1)                                        C.sub.1g                                                                            -3763(4) 1733(5)   3232(3) 44(1)                                        C.sub.2g                                                                            -4097(5) 2625(6)   3907(4) 57(2)                                        C.sub.3g                                                                            -3524(5) 2241(6)   4845(3) 57(2)                                        C.sub.4g                                                                            -2319(5) 1977(6)   4633(3) 50(2)                                        ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i    the last significant digit.                                                    .sup.b Atoms are labeled in agreement with FIG. 1.                            .sup.c This is onethird of the trace of the orthogonalized B.sub.ij           tensor.                                                                       .sup.d This is a symmetryrequired value and is therefore listed without a    estimated standard deviation.                                             

                  TABLE II                                                        ______________________________________                                        Anisotropic Thermal Parameters for Nonhydrogen Atoms                          in Crystalline [Cr.sub.5 (NC.sub.4 H.sub.4).sub.10 (OC.sub.4 H.sub.8).sub.    4 ]                                                                           Atom   Anisotropic Thermal Parameter (Å × 10)                       Type.sup.c                                                                           B.sub.11                                                                             B.sub.22                                                                              B.sub.33                                                                           B.sub.12                                                                             B.sub.13                                                                              B.sub.23                            ______________________________________                                        Cr.sub.1                                                                             20(1)  23(1)   32(1)                                                                               5(1)  5(1)    -4(1)                               Cr.sub.2                                                                             23(1)  22(1)   27(1)                                                                               7(1)  3(1)    -2(1)                               Cr.sub.3                                                                             27(1)  26(1)   34(1)                                                                              11(1)  8(1)     1(1)                               N.sub.1a                                                                             21(1)  27(1)   29(1)                                                                               8(1)  1(1)    -2(1)                               C.sub.1a                                                                             28(2)  31(2)   30(2)                                                                               4(1)  8(1)    -4(1)                               C.sub.2a                                                                             23(2)  49(2)   49(2)                                                                               8(2)  5(2)    -16(2)                              C.sub.3a                                                                             31(2)  51(2)   52(2)                                                                              22(2)  -7(2)   -11(2)                              C.sub.4a                                                                             36(2)  32(2)   34(2)                                                                              15(1)  -2(1)   -3(1)                               N.sub.1b                                                                             24(1)  25(1)   35(1)                                                                               3(1)  5(1)    -4(1)                               C.sub.1b                                                                             40(2)  31(2)   33(2)                                                                               2(1)  11(1)   -1(1)                               C.sub.2b                                                                             46(2)  42(2)   54(2)                                                                              -7(2)  24(2)   -5(2)                               C.sub.3b                                                                             25(2)  50(2)   71(3)                                                                              -3(2)  15(2)   -27(2)                              C.sub.4b                                                                             29(2)  38(2)   48(2)                                                                              10(1)  0(2)    -15(2)                              N.sub.1c                                                                             28(1)  25(1)   30(1)                                                                              11(1)  3(1)    -2(1)                               C.sub.1c                                                                             36(2)  35(2)   31(2)                                                                              10(1)  4(1)    -3(1)                               C.sub.2c                                                                             52(2)  34(2)   43(2)                                                                              13(2)  6(2)    -13(1)                              C.sub.3c                                                                             51(2)  31(2)   50(2)                                                                              22(2)  5(2)    -5(2)                               C.sub.4c                                                                             35(2)  34(2)   31(2)                                                                              16(1)  4(1)     1(1)                               N.sub.1d                                                                             32(1)  23(1)   31(1)                                                                              12(1)  6(1)     3(1)                               C.sub.1d                                                                             33(2)  32(2)   42(2)                                                                               9(-)  6(2)    -0(1)                               C.sub.2d                                                                             36(2)  50(2)   59(2)                                                                              24(2)  6(2)     11(2)                              C.sub.3d                                                                             61(3)  44(2)   47(2)                                                                              36(2)  11(2)    3(2)                               C.sub.4d                                                                             49(2)  35(2)   31(2)                                                                              23(2)  4(2)     1(1)                               N.sub.1e                                                                             36(2)  30(1)   42(2)                                                                              13(1)  14(1)    4(1)                               C.sub.1e                                                                             46(2)  36(2)   46(2)                                                                              20(2)  10(2)    6(2)                               C.sub.2e                                                                             64(3)  30(2)   37(2)                                                                              15(2)  7(2)     4(1)                               C.sub.3e                                                                             55(3)  31(2)   46(2)                                                                              -1(2)  18(2)   -0(2)                               C.sub.4e                                                                             39(2)  38(2)   62(2)                                                                               9(2)  17(2)   10 4(2)                             O.sub.1f                                                                             29(1)  25(1)   40(1)                                                                               6(1)  -1(1)   -2(1)                               C.sub.1f                                                                             34(2)  44(2)   45(2)                                                                               9(2)  -8(2)   -6(2)                               C.sub.2f                                                                             45(3)  67(3)   95(4)                                                                              -(2)   -15(3)  -6(3)                               C.sub.3f                                                                             59(3)  34(2)   78(3)                                                                              -2(2)  -6(3)   -9(2)                               C.sub.4f                                                                             45(2)  23(1)   48(2)                                                                               7(1)  6(2)    -1(1)                               O.sub.1g                                                                             34(1)  41(1)   37(1)                                                                              19(1)  7(1)    -1(1)                               C.sub.1g                                                                             31(2)  56(2)   50(2)                                                                              20(2)  4(2)    -5(2)                               C.sub.2g                                                                             47(3)  65(3)   72(3)                                                                              35(2)  2(2)    -12(2)                              C.sub.3g                                                                             60(3)  75(3)   50(2)                                                                              36(2)  16(2)   -8(2)                               C.sub.4g                                                                             45(2)  77(3)   35(2)                                                                              27(2)  8(2)    -5(2)                               ______________________________________                                         .sup.a The number in parentheses are the estimated standard deviations in     the last significant digit.                                                   .sup.b The form of the anisotropic thermal parameter is given in referenc    8 on page 6 of the structure report.                                           .sup.c Atoms are labeled in agreement with FIG. 1.                       

                  TABLE III                                                       ______________________________________                                        Atomic Coordinates for Hydrogen Atoms in Crystalline                          [Cr.sub.5 (NC.sub.4 H.sub.4).sub.10 (OC.sub.4 H.sub.8).sub.4 ].sup.a          Atom    Fractional Coordinates                                                Type.sup.b                                                                            10.sup.4 x    10.sup.4 y                                                                             10.sup.4 z                                     ______________________________________                                        H.sub.1a                                                                              -2129         -661     1707                                           H.sub.2a                                                                              -4154         -55      1219                                           H.sub.3a                                                                              -3608         1937     -69                                            H.sub.4a                                                                              -1267         2508     -339                                           H.sub.1b                                                                               1053         3405     -617                                           H.sub.2b                                                                               3405         4593     -834                                           H.sub.3b                                                                               4676         3202      189                                           H.sub.4b                                                                               3031         1158     1020                                           H.sub.1c                                                                               1013         3445     3687                                           H.sub.2c                                                                                364         5592     3881                                           H.sub.3c                                                                              -1331         5685     2512                                           H.sub.4c                                                                              -1704         3580     1540                                           N.sub.1d                                                                               1881         1460     3743                                           N.sub.2d                                                                               3177         -88      3396                                           N.sub.3d                                                                               1807         -1790    2120                                           N.sub.4d                                                                               -291         -1252    1752                                           N.sub.1e                                                                               -446         -1976    3968                                           N.sub.2e                                                                              -1997         -4161    4742                                           N.sub.3e                                                                              -4139         -3699    4803                                           N.sub.4e                                                                              -3878         - 1286   4012                                           N.sub.1fa                                                                              3351         3836     3136                                           N.sub.1fb                                                                              3882         3308     2299                                           N.sub.2fa                                                                              5068         5771     2893                                           N.sub.2fb                                                                              4965         5524     1806                                           N.sub.3fa                                                                              3462         6711     2728                                           N.sub.3fb                                                                              4068         7245     1757                                           H.sub.4fa                                                                              2417         5653      964                                           H.sub.4fb                                                                              1641         5625     1839                                           H.sub.1ga                                                                             -3631         2231     2623                                           H.sub.1gb                                                                             -4455          813     3162                                           H.sub.2ga                                                                             -5037         2381     3901                                           H.sub.2gb                                                                             -3704         3640     3750                                           H.sub.3ga                                                                             -4129         1385     5124                                           H.sub.3gb                                                                             -3307         3025     5266                                           H.sub.4ga                                                                             -2173         1220     5050                                           H.sub.4ga                                                                             -1565         2846     4703                                           ______________________________________                                         .sup.a Hydrogen atoms were included in the structure factor calculations      as idealized atoms (assuming sp.sup.2 or sp.sup.3hybridization of the         carbon atoms and a C--H bond length of 0.96Å) "riding" on their           respective carbon atoms. The isotropic thermal parameter of each hydrogen     atom was fixed at 1.2 times the equivalent isotropic thermal parameter of     the carbon atom to which it is covalently bonded                              .sup.b Hydrogen atoms are labeled with the same numerical and literal         subscripts as their carbon atoms with an additional literal subscript (a      or b) where necessary to distinquish between hydrogen atoms bonded to the     same carbon.                                                             

                  TABLE IV                                                        ______________________________________                                        Bond Lengths Involving Nonhydrogen Atoms in Crystalline                       [Cr.sub.5 (NC.sub.4 H.sub.4).sub.10 (OC.sub.4 H.sub.8).sub.4 ].sup.a          Type.sup.b                                                                              Length, Å                                                                              Type.sup.b                                                                             Length, Å                                 ______________________________________                                        Cr.sub.1 . . . Cr.sub.2                                                                 3.066(1)     O.sub.1f -C.sub.1f                                                                     1.451(5)                                      Cr.sub.2 . . . Cr.sub.3                                                                 3.121(1)     O.sub.1f -C.sub.4f                                                                     1.453(5)                                                             O.sub.1g -C.sub.1g                                                                     1.448(6)                                      Cr.sub.1 -N.sub.1a                                                                      2.153(3)     O.sub.1g -C.sub.4g                                                                     1.451(5)                                      Cr.sub.1 -N.sub.1b                                                                      2.092(3)                                                            Cr.sub.2 -N.sub.1a                                                                      2.178(3)     C.sub.1a -C.sub.2a                                                                     1.360(6)                                      Cr.sub.2 -N.sub.1b                                                                      2.149(3)     C.sub.2a -C.sub.3a                                                                     1.395(6)                                      Cr.sub.2 -N.sub.1c                                                                      2.112(4)     C.sub.3a -C.sub.4a                                                                     1.351(6)                                      Cr.sub.3 -N.sub.1c                                                                      2.172(3)     C.sub.1b -C.sub.2b                                                                     1.338(6)                                      Cr.sub.3 -N.sub.1d                                                                      2.101(4)     C.sub.2b -C.sub.3b                                                                     1.393(7)                                      Cr.sub.3 -N.sub.1e                                                                      2.037(3)     C.sub.3b -C.sub.4b                                                                     1.376(6)                                                             C.sub.1c -C.sub.2c                                                                     1.365(7)                                      Cr.sub.2 -O.sub.1f                                                                      2.082(2)     C.sub.2c -C.sub.3c                                                                     1.400(6)                                      Cr.sub.3 - O.sub.1g                                                                     2.068(3)     C.sub.3c -C.sub.4c                                                                     1.356(6)                                                             C.sub.1d -C.sub.2d                                                                     1.376(7)                                      N.sub.1a -C.sub.1a                                                                      1.399(4)     C.sub.2d -C.sub.3d                                                                     1.396(6)                                      N.sub.1a -C.sub.4a                                                                      1.397(5)     C.sub.3d -C.sub.4d                                                                     1.367(8)                                      N.sub.1b -C.sub.1b                                                                      1.398(5)     C.sub.1e -C.sub.2e                                                                     1.370(5)                                      N.sub.1b -C.sub.4b                                                                      1.379(6)     C.sub.2e -C.sub.3e                                                                     1.374(8)                                      N.sub.1c -C.sub.1c                                                                      1.388(4)     C.sub.3e -C.sub.4e                                                                     1.366(6)                                      N.sub.1c -C.sub.4c                                                                      1.394(6)                                                            N.sub.1d -C.sub.1d                                                                      1.349(5)     C.sub.1f -C.sub.2f                                                                     1.460(6)                                      N.sub.1d -C.sub.4d                                                                      1.377(5)     C.sub.2f -C.sub.3f                                                                     1.474(9)                                      N.sub.1e -C.sub.1e                                                                      1.370(6)     C.sub.3f -C.sub.4f                                                                     1.496(6)                                      N.sub.1e -C.sub.4e                                                                      1.361(6)     C.sub.1g -C.sub.2g                                                                     1.496(8)                                                             C.sub.2g -C.sub.3g                                                                     1.485(7)                                                             C.sub.3g -C.sub.4g                                                                     1.476(9)                                      ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i    the last significant digit.                                                    .sup.b Atoms are labeled in agreement with FIG. 1.                       

                  TABLE V                                                         ______________________________________                                        Bond Angles Involving Nonhydrogen Atoms in Crystalline                        [Cr.sub.5 (NC.sub.4 H.sub.4).sub.10 (OC.sub.4 H.sub.8).sub.4 ].sup.a          Type.sup.b                                                                              Angle, deg   Type.sup.b                                                                              Angle, deg                                   ______________________________________                                        N.sub.1a Cr.sub.1 N.sub.1b                                                               84.8(1)     Cr.sub.1 N.sub.1a Cr.sub.2                                                               90.2(1)                                     N.sub.1a Cr.sub.1 N.sub.1a,.sup.c                                                        .sup. 180.0(--).sup.d                                                                     Cr.sub.1 N.sub.1a C.sub.1a                                                              121.2(2)                                     N.sub.1b Cr.sub.1 N.sub.1a,.sup.c                                                        95.2(1)     Cr.sub.2 N.sub.1a C.sub.1a                                                              110.0(2)                                     N.sub.1b Cr.sub.1 N.sub.1b,.sup.c                                                        .sup. 180.0(--).sup.d                                                                     Cr.sub.1 N.sub.1a C.sub.4a                                                              113.4(2)                                                            Cr.sub.2 H.sub.1a C.sub.4a                                                              110.6(2)                                     N.sub.1a Cr.sub.2 N.sub.1b                                                               82.9(1)     C.sub.1a N.sub.1a C.sub.4a                                                              103.5(3)                                     N.sub.1a Cr.sub.2 N.sub.1c                                                               96.5(1)     Cr.sub.1 N.sub.1b Cr.sub.2                                                               92.6(1)                                     N.sub.1b Cr.sub.2 N.sub.1c                                                              168.9(1)     Cr.sub.1 N.sub.1b C.sub.1b                                                              117.9(2)                                     N.sub.1a Cr.sub.2 O.sub.1f                                                              162.4(1)     Cr.sub.2 N.sub.1b C.sub.1b                                                              107.6(3)                                     N.sub.1b Cr.sub.2 O.sub.1f                                                               89.5(1)     Cr.sub.1 N.sub.1b C.sub.4b                                                              120.6(3)                                     N.sub.1c Cr.sub.2 O.sub.1f                                                               87.9(1)     Cr.sub.2 N.sub.1b C.sub.4b                                                              113.0(3)                                                            C.sub.1b H.sub.1b C.sub.4b                                                              104.4(3)                                     N.sub.1c Cr.sub.3 N.sub.1d                                                               88.1(1)     Cr.sub.2 N.sub.1c Cr.sub.3                                                               93.5(1)                                     N.sub.1c Cr.sub.3 N.sub.1e                                                              176.5(1)     Cr.sub.2 N.sub.1c C.sub.1c                                                              121.4(3)                                     N.sub.1d Cr.sub.3 N.sub.1e                                                               93.5(1)     Cr.sub.3 N.sub.1c C.sub.1c                                                              100.0(2)                                     N.sub.1c Cr.sub.3 O.sub.1g                                                               88.8(1)     Cr.sub.2 N.sub.1c C.sub.4c                                                              116.1(2)                                     N.sub.1d Cr.sub.3 O.sub.1g                                                              170.4(1)     Cr.sub.3 N.sub.1c C.sub.4c                                                              121.5(2)                                     N.sub.1e Cr.sub.3 O.sub.1g                                                               89.1(1)     C.sub.1c N.sub.1c C.sub.4c                                                              104.2(3)                                                            Cr.sub.3 H.sub.1d C.sub.1d                                                              121.3(3)                                     N.sub.1a C.sub.1a C.sub.2a                                                              110.6(3)     Cr.sub.3 N.sub.1d C.sub.4d                                                              127.8(3)                                     C.sub.1a C.sub.2a C.sub.3a                                                              107.5(4)     C.sub.1d N.sub.1d C.sub.4d                                                              106.4(4)                                     C.sub.2a C.sub.3a C.sub.4a                                                              106.9(4)     Cr.sub.3 N.sub.1e C.sub.1e                                                              126.3(3)                                     C.sub.3a C.sub.4a N.sub.1a                                                              111.5(3)     Cr.sub.3 N.sub.1e C.sub.4e                                                              128.3(3)                                     N.sub.1b C.sub.1b C.sub.2b                                                              111.2(4)     C.sub.1e N.sub.1e C.sub.4e                                                              105.3(3)                                     C.sub. 1b C.sub.2b C.sub.3b                                                             107.4(4)                                                            C.sub.2b C.sub.3b C.sub.4b                                                              107.0(4)     Cr.sub.2 O.sub.1f C.sub.1f                                                              131.5(2)                                     C.sub.3b C.sub.4b N.sub.1b                                                              110.1(4)     Cr.sub.2 O.sub.1f C.sub.4f                                                              118.9(2)                                     N.sub.1c C.sub.1c C.sub.2c                                                              110.9(4)     C.sub.1f O.sub.1f C.sub.4f                                                              109.1(3)                                     C.sub.1c C.sub.2c C.sub.3c                                                              106.8(4)     Cr.sub.3 O.sub.1g C.sub.1g                                                              131.9(3)                                     C.sub.2c C.sub.3c C.sub.4c                                                              107.2(4)     Cr.sub.3 O.sub.1g C.sub.4g                                                              118.6(3)                                     C.sub.3c C.sub.4c N.sub.1c                                                              110.9(3)     C.sub.1g O.sub.1g C.sub.4g                                                              109.5(4)                                     N.sub.1d C.sub.1d C.sub.2d                                                              110.3(4)                                                            C.sub.1d C.sub.2d C.sub.3d                                                              106.7(4)     O.sub.qf C.sub.1f C.sub.2f                                                              105.0(4)                                     C.sub.2d C.sub.3d C.sub.4d                                                              106.6(5)     C.sub.1f C.sub.2f C.sub.3f                                                              104.9(4)                                     C.sub.3d C.sub.4d N.sub.1d                                                              109.9(3)     C.sub.2f C.sub.3f C.sub.4f                                                              104.4(4)                                     N.sub.1e C.sub.1e C.sub.2e                                                              110.0(4)     C.sub.3f C.sub.4f O.sub.1f                                                              105.4(4)                                     C.sub.1e C.sub.2e C.sub.3e                                                              107.2(4)     O.sub.1g C.sub.1g C.sub.2g                                                              104.8(4)                                     C.sub.2e C.sub.3e C.sub.4e                                                              106.7(4)     C.sub.1g C.sub.2g C.sub.3g                                                              104.2(5)                                     C.sub.3e C.sub.4e N.sub.1e                                                              110.8(5)     C.sub.2g C.sub.3g C.sub.4g                                                              104.2(4)                                                            C.sub.3g C.sub. 4g O.sub.1g                                                             106.1(4)                                     ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i    the last significant digti.                                                    .sup.b Atoms are labeled in agreement with FIG. 1.                            .sup.c Atoms labeled with a prime () are related to nonprimed atoms by th    symmetry operation -x, -y, -z where the fractional coordinates (x,y,z) are     given in Table I.                                                             .sup.d This is a symmetryrequired value and is therefore listed without a    estimated standard deviation.                                             

EXAMPLE V

A single crystal x-ray structure was obtained for Cr(NC₄ H₄)₄, a portionof Product III and shown in FIG. 3. A single crystal x-ray structure wasobtained for [Na]₂ [Cr(NC₄ H₄)₄ ].2(OC₄ H₈), Product III and shown inFIG. 4. Thedescription of the single-crystal sample and mounting usedfor the data collection are as follows:

Color: Red-Orange

Shape: Rectangular parallelepiped

Dimensions: 0.50×0.55×0.65 mm

Crystal Mount: Crystal was glued to the inside of a thin-walled glasscapillary and sealed under N₂.

Crystal Orientation: Crystal was oriented with its longest edge nearlyparallel to the phi axis of the diffractometer.

Width at Half-height from ω Scans: 0.86°

The space group and cell data are as follows:

Crystal System: Monoclinic

Space Group and Number:² C2/c-C_(2h) ⁶ (no. 15)

Number of Computer-Centered Reflections Used in the Least-SquaresRefinement of the Cell Dimensions: ##EQU2##Lattice Constants with esd's:

    ______________________________________                                        a = 9.522(2)Å                                                                           α = 90.00°                                                                   V = 2697(1)Å.sup.3                              b = 15.118(2)Å                                                                          β = 98.99(1)°                                                                 Z = 4                                               c = 18.967(3)Å                                                                          γ = 90.00°                                                                   λ= 0.71073Å                              ______________________________________                                    

Molecular Weight: 506.52 amu

Calculated Density: 1.248 g/cm⁻³

Linear Absorption Coefficient:^(3a) 0.47 mm⁻¹

Tables VI-X list the resultant parameters used to generate the molecularstructures shown in FIGS. 3 and 4.

                  TABLE VI                                                        ______________________________________                                        Atomic Coordinates for Nonhydrogen Atoms in Crystalline                       (Na).sub.2 {Cr(NC.sub.4 H.sub.4).sub.4 }-2OC.sub.4 H.sub.4,.sup.a                                       Equivalent Isotropic                                Atom   Fractional Coordinates                                                                           Thermal Parameter,                                  Type.sup.b                                                                           10.sup.4 x                                                                             10.sup.4 y                                                                              10.sup.4 z                                                                          B, Å.sup.2 × 10.sup.c               ______________________________________                                        Anion                                                                         Cr     0.sup.d  2982(1)   2580.sup.d                                                                          50(1)                                         N.sub.1                                                                              1981(4)  2924(2)   3183(2)                                                                             56(1)                                         N.sub.2                                                                              0.sup.d  4343(3)   2580.sup.d                                                                          52(1)                                         N.sub.3                                                                              0.sup.d  1612(3)   2580.sup.d                                                                          70(2)                                         C.sub.11                                                                             3241(5)  2950(3)   3008(3)                                                                             65(2)                                         C.sub.12                                                                             4224(6)  2769(3)   3587(3)                                                                             73(2)                                         C.sub.13                                                                             3513(7)  2638(4)   4146(3)                                                                             82(2)                                         C.sub.14                                                                             2094(7)  2734(4)   3884(3)                                                                             76(2)                                         C.sub.21                                                                              987(5)  4884(3)   2926(3)                                                                             60(1)                                         C.sub.22                                                                              582(4)  5753(3)   2766(3)                                                                             69(2)                                         C.sub.31                                                                              390(5)  1081(3)   1996(4)                                                                             94(2)                                         C.sub.32                                                                              236(7)   213(3)   2189(5)                                                                             133(6)                                        Cation                                                                        Na     2301(2)  6879(1)   1783(1)                                                                             69(1)                                         Solvent of Crystallization                                                    O.sub.1                                                                              2065(4)  5108(2)    830(2)                                                                             83(1)                                         C.sub.41                                                                              2759(11)                                                                              5174(5)    239(4)                                                                             143(4)                                        C.sub.42                                                                              2884(11)                                                                              4319(5)   -79(4)                                                                              148(4)                                        C.sub.43                                                                              1893(10)                                                                              3786(5)    264(5)                                                                             142(4)                                        C.sub.44                                                                             1699(9)  4231(4)    902(4)                                                                             120(3)                                        ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i    the last significant digit.                                                    .sup.b Atoms are labeled in agreement with FIGS. 3 and 4.                     .sup.c This is onethird of the trace of the orthogonalized B.sub.ij           tensor.                                                                       .sup.d This is a symmetryrequired value and is therefore listed without a    estimated standard deviation.                                             

                  TABLE VII                                                       ______________________________________                                        Anisotropic Thermal Parameters for Nonhydrogen Atoms in                       Crystalline {Na}.sub.2 {Cr(NC.sub.4 H.sub.4).sub.4 }-2 OC.sub.4 H.sub.8.su    p.a,b                                                                         Atom  Anisotropic Thermal Parameters (Å.sup.2 × 10)                 Type.sup.c                                                                          B.sub.11                                                                              B.sub.22                                                                              B.sub.33                                                                             B.sub.12                                                                             B.sub.13                                                                             B.sub.23                           ______________________________________                                        Anion                                                                         Cr     64(1)   34(1)   55(1) 0.sup.d                                                                              15(1)  0.sup.d                            N.sub.1                                                                              69(2)   44(2)   56(2)  6(1)  12(1)    6(1)                             N.sub.2                                                                              64(3)   39(2)   56(3) 0.sup.d                                                                              16(2)  0.sup.d                            N.sub.3                                                                              65(3)   39(2)  107(4) 0.sup.d                                                                              14(3)  0.sup.d                            C.sub.11                                                                             79(3)   50(2)   70(3) -6(2)  18(2)    2(2)                             C.sub.12                                                                             70(3)   62(3)   94(3)  4(2)   7(2)   -9(2)                             C.sub.13                                                                            103(4)   79(3)   59(3)  22(3) -8(3)    0(2)                             C.sub.14                                                                             86(3)   96(3)   59(3)  16(3) 16(2)    5(2)                             C.sub.21                                                                             66(2)   45(2)   70(3) -2(2)  15(2)   -6(2)                             C.sub.22                                                                             68(3)   38(2)  105(4) -7(2)  27(2)   -9(2)                             C.sub.31                                                                             65(3)   61(3)  152(5)  6(2)   9(3)  -36(3)                             C.sub.32                                                                             71(5)   46(2)  266(15)                                                                               6(3)  -20(6) -44(4)                             Cation                                                                        Na     70(1)   57(1)  81(1)  -2(1)  15(1)  -15(1)                             Solvent of Crystallization                                                    O.sub.1                                                                             100(2)   65(2)   82(2) -10(2) 39(2)  -16(2)                             C.sub.41                                                                            222(8)  112(5)  116(5) -46(5) 92(6)  -22(4)                             C.sub.42                                                                            192(8)  160(8)  107(5)  12(6) 70(5)  -32(5)                             C.sub.43                                                                            147(6)  109(6)  177(8) -27(5) 48(6)  -69(6)                             C.sub.44                                                                            177(6)   77(4)  124(5) -21(4) 76(5)  -14(3)                             ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i    the last significant digit.                                                    .sup.b The form of the anisotropic thermal parameter is given in referenc    8 on page 6 of the structure report.                                           .sup.c Atoms are labeled in agreement with Figures 3 and 4.                   .sup.d This is a symmetryrequired value and is therefore listed without a    estimated standard deviation.                                             

                  TABLE VIII                                                      ______________________________________                                        Atomic Coordinates for Hydrogen Atoms in Crystalline                          (Na).sub.2 {Cr(NC.sub.4 H.sub.4).sub.4 }-2(OC.sub.4 H.sub.8).sup.a            Atom      Fractional Coordinates                                              Type.sup.b                                                                              10.sup.4 x 10.sup.4 y  10.sup.4 z                                   ______________________________________                                        Anion                                                                         H.sub.11  3456       3881        2541                                         H.sub.12  5233       2748        3680                                         H.sub.13  3922       2488        4628                                         H.sub.14  1341       2679        4164                                         H.sub.21  1665       4697        3285                                         H.sub.22  1071       6262        2985                                         H.sub.31   706       1274        1565                                         H.sub.32   493       -301        1937                                         Solvent of Crystallization                                                    H.sub.41a 2250       5576        -100                                         H.sub.41b 3710       5388         -1                                          H.sub.42b 2464       4348        -538                                         H.sub.43a  995       3707        -39                                          H.sub.43b 2326       3220         377                                         H.sub.44a 2295       3973        1304                                         H.sub.44b  723       4191         969                                         ______________________________________                                         .sup.a Hydrogen atoms were included in the structure factor calculations      as indicated atoms (assuming sp.sup.2 or sp.sup.3hybridization of the         carbon atoms and C--H bond length of 0.9610 "riding" on their respective      carbon atoms. The isotropic thermal parameter of each hydrogen atom was       fixed at 1.2 times the equivalent isotropic thermal parameter of the          carbon atom to which it is covalently bonded.                                 .sup.b Hydrogen atoms are labeled with the same numerical subscripts as       the carbon atoms to which they are covalently bonded with an additional       literal subscript (a or b) where necessary to distinguish between             hydrogwns bonded to the same carbon.                                     

                  TABLE IX                                                        ______________________________________                                        Anion Bond Lengths and Bond Angles Involving Nonhydrogen                      Atoms in Crystalline {Na}.sub.2 {Cr(HC.sub.4 H.sub.4).sub.4 }-2OC.sub.4       H.sub.8.sup.a                                                                 Type.sup.b                                                                              Length, Å                                                                              Type.sup.b                                                                              Length, Å                                ______________________________________                                        Cr--N.sub.1                                                                             2.057(3)     C.sub.11 --C.sub.12                                                                     1.355(7)                                     Cr--N.sub.2                                                                             2.056(4)     C.sub.12 --C.sub.13                                                                     1.361(9)                                     Cr--N.sub.3                                                                             2.072(5)     C.sub.13 --C.sub.14                                                                     1.374(9)                                                            C.sub.21 --C.sub.22                                                                     1.372(6)                                     N.sub.1 --C.sub.11                                                                      1.369(7)     C.sub.22 --C.sub.22 '.sup.c                                                             1.379(9)                                     N.sub.1 --C.sub.14                                                                      1.344(6)     C.sub.31 --C.sub.32                                                                     1.376(7)                                     N.sub.2 --C.sub.21                                                                      1.360(5)     C.sub.32 --C.sub.32 '.sup.c                                                              1.327(18)                                   N.sub.3 --C.sub.31                                                                      1.344(7)                                                            ______________________________________                                        Type.sup.b                                                                              Angle, deg.  Type.sup.b                                                                              Angle, deg.                                  ______________________________________                                        N.sub.1 CrN.sub.2                                                                        92.5(1)     N.sub.1 C.sub.11 C.sub.12                                                               110.5(5)                                     N.sub.1 CrN.sub.3                                                                        87.5(1)     C.sub.11 C.sub.12 C.sub.13                                                              107.3(5)                                     N.sub.1 CrN.sub.1 '.sup.c                                                               175.1(2)     C.sub.12 C.sub.13 C.sub.14                                                              106.4(5)                                     N.sub.2 CrN.sub.3                                                                       180.0(-).sup.d                                                                             N.sub.1 C.sub.14 C.sub.13                                                               110.9(5)                                                            N.sub.2 C.sub.21 C.sub.22                                                               110.2(4)                                     CrN.sub.1 C.sub.11                                                                      127.5(3)     C.sub.21 C.sub.22 C.sub.22 '.sup.c                                                      106.8(3)                                     CrN.sub.1 C.sub.14                                                                      127.1(4)     N.sub.3 C.sub.31 C.sub.32                                                               109.1(6)                                     C.sub.11 N.sub.1 C.sub.14                                                               104.9(4)     C.sub.31 C.sub.32 C.sub.32 '.sup.c                                                      107.5(5)                                     CrN.sub.2 C.sub.21                                                                      127.0(2)                                                            C.sub.21 N.sub.2 C.sub.21 '.sup.c                                                       104.0(5)                                                            CrN.sub.3 C.sub.31                                                                      126.7(3)                                                            C.sub.31 N.sub.3 C.sub.31 '.sup.c                                                       104.7(6)                                                            ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i    the last significant digit.                                                    .sup.b Atoms are labeled in agreement with Figure 4.                          .sup.c Atoms labeled with a prime(') are related to nonprimed atoms by th    symmetry operation -x, y, 1/2-z.                                          

                  TABLE X                                                         ______________________________________                                        Bond Lengths and Angles Lavolving the Nonhydrogen Atoms                       of the Cation and Solvent of Crystallization                                  is {Na}.sub.2 {Cr(NC.sub.4 H.sub.4).sub.4 }-2(OC.sub.4 H.sub.8).sup.a         Type.sup.b                                                                              Length, Å                                                                              Type.sup.b                                                                              Length, Å                                ______________________________________                                        Na--O.sub.1                                                                             2.313(4)     O.sub.1 --C.sub.41                                                                      1.390(10)                                                           O.sub.1 --C.sub.44                                                                      1.382(7)                                     Na . . . N.sub.1 ".sup.c                                                                2.888(4(                                                            Na . . . N.sub.3 ".sup.c                                                                2.830(4)     C.sub.41 --C.sub.42                                                                     1.43(1)                                                             C.sub.42 --C.sub.43                                                                     1.42(1)                                                             C.sub.43 --C.sub.44                                                                     1.42(1)                                      ______________________________________                                        Type.sup.b                                                                              Angle, deg.  Type.sup.b                                                                              Angle, deg.                                  ______________________________________                                        O.sub.1 NaN.sub.1 ".sup.c                                                               128.6(3)     C.sub.41 O.sub.1 C.sub.44                                                               107.9(5)                                     O.sub.1 NaN.sub.3 ".sup.c                                                               121.8(3)                                                            N.sub.1 "NaN.sub.3 ".sup.c                                                               59.9(3)     O.sub.1 C.sub.41 C.sub.42                                                               109.0(7)                                                            C.sub.41 C.sub.42 C.sub.43                                                              105.0(8)                                     NaO.sub.1 C.sub.41                                                                      125.7(4)     C.sub.42 C.sub.43 C.sub.44                                                              107.0(7)                                     NaO.sub.1 C.sub.44                                                                      121.8(4)     O.sub.1 C.sub.44 C.sub.43                                                               107.6(7)                                     ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i    the last significant digit.                                                    .sup.b Atoms are labeled in agreement with Figure 4.                          .sup.c Atoms labeled a double prime(") are related to nonprinted atoms by     the symmetry operation 1/2-x, 1/2-y, 1/2-z.                              

EXAMPLE VI

Single crystal x-ray structures were obtained for [Cr(NC₄ H₄)₅ (OC₄H₈)], shown in FIG. 5, and [Cr(NC₄ H₄)₅ (OC₄ H₈)][Na]₂.4(OC₄ H₈),Product IV, and shown in FIG. 6. The description of the single-crystalsample and mounting used for data collection are as follows:

Color: Purple

Shape: Rectangular parallelepiped

Dimensions: 0.50×0.55×0.63 mm

Crystal Mount: Crystal was glued to the inside of a thin-walled glasscapillary and sealed under N₂.

Crystal Orientation: Crystal was oriented with its longest edge nearlyparallel to the phi axis of the diffractometer.

Width at Half-height from ω Scans: 0.42°

The space group and cell data are as follows:

Crystal System: Monoclinic

Space Group and Number:² P2₁ -C₂ ² (No. 4)

Number of Computer-Centered Reflections Used in the Least-SquaresRefinement of the Cell Dimensions: ##EQU3##Lattice Constants with esd's:

    ______________________________________                                        a = 10.042(2)Å                                                                           α = 90.00°                                                                     V = 2162(1)Å.sup.3                           b = 17.242(4)Å                                                                           β = 106.54(2)°                                                                  Z = 2                                            c = 13.025(3)Å                                                                           γ = 90.00°                                                                     λ= 0.71073Å                           ______________________________________                                    

Molecular Weight=788.93 amu

Calculated Density: 1.212 g/cn⁻³

Linear Absorption Coefficient: 3a 0.32 mm⁻¹

Tables XI-XV list the resultant parameters used to generate themolecular structures shown in FIGS. 5 and 6.

                  TABLE XI                                                        ______________________________________                                        Atomic Coordinates for Nonhydrogen Atoms in Crystalline                       [Cr(NC.sub.4 H.sub.4).sub.5 (OC.sub.4 H.sub.8)](Na)-4(OC.sub.4 H.sub.8)                                    Equivalent Iso-                                                               tropic Thermal                                   Atom    Fractional Coordinates                                                                             Parameter,                                       Type.sup.b                                                                            10.sup.4 x                                                                              10.sup.4 y                                                                             10.sup.4 z                                                                            B, Å.sup.2 × 10.sup.c            ______________________________________                                        Anion                                                                         Cr      198(1)    1477     2531(1) 32(1)                                      N.sub.1a                                                                              1694(5)   2026(3)  2028(4) 40(2)                                      C.sub.1a                                                                              1749(7)   2782(4)  1742(6) 48(2)                                      C.sub.2a                                                                              2929(8)   2926(5)  1420(7) 66(3)                                      C.sub.3a                                                                              3661(7)   2236(5)  1554(6) 62(3)                                      C.sub.4a                                                                              2899(6)   1695(5)  1913(5) 52(2)                                      N.sub.1b                                                                              1651(5)   1087(3)  3885(4) 40(2)                                      C.sub.1b                                                                              1463(8)   560(4)   4575(5) 48(2)                                      C.sub.2b                                                                              2572(9)   518(6)   5423(8) 82(4)                                      C.sub.3b                                                                              3534(8)   1064(6)  5275(6) 70(3)                                      C.sub.4b                                                                              2952(6)   1382(5)  4340(5) 48(2)                                      N.sub.1c                                                                              -1326(5)  1888(3)  1250(4) 38(2)                                      C.sub. 1c                                                                             -1200(8)  2172(4)  266(6)  51(2)                                      C.sub.2c                                                                              -2458(8)  2270(5)  -476(6) 58(3)                                      C.sub.3c                                                                              -3435(8)  2038(6)  56(7)   75(3)                                      C.sub.4c                                                                              -2710(7)  1826(5)  1091(6) 56(3)                                      N.sub.1d                                                                              -32(5)    2455(4)  3445(5) 43(2)                                      C.sub.1d                                                                              504(7)    2562(5)  4505(6) 49(2)                                      C.sub.2d                                                                              107(9)    3278(5)  4774(8) 72(3)                                      C.sub.3d                                                                              -698(8)   3629(5)  3832(6) 59(3)                                      C.sub.4d                                                                              -769(7)   3106(4)  3055(6) 52(2)                                      N.sub.1e                                                                              315(5)    505(4)   1690(4) 40(2)                                      C.sub.1e                                                                              -574(8)   277(5)   704(6)  55(3)                                      C.sub.2e                                                                              -197(10)  -432(5)  403(7)  67(3)                                      C.sub.3e                                                                              990(10)   -662(6)  1256(8) 79(4)                                      C.sub.4e                                                                              -1265(8)  -92(4)   2016(7) 51(3)                                      O.sub.1f                                                                              -1356(4)  926(3)   3063(4) 43(1)                                      C.sub.1f                                                                              -2047(7)  1244(5)  3800(6) 57(3)                                      C.sub.2f                                                                              -3263(10) 713(6)   3706(9) 98(5)                                      C.sub.3f                                                                              -2833(11) -21(6)   3402(8) 93(4)                                      C.sub.4f                                                                              -1903(8)  171(5)   2724(7) 64(3)                                      Cation 1                                                                      Na.sub.1                                                                              2254(3)   3336(2)  3737(3) 75(1)                                      Cation 2                                                                      Na.sub.2                                                                              1430(3)   974(2)   126(2)  62(1)                                      Solvent Molecules of Crystallization                                          O.sub.1g                                                                              4576(6)   3329(4)  4706(5) 83(2)                                      C.sub.1g                                                                              5748(9)   3100(10) 4433(9) 125(6)                                     C.sub.2g                                                                              6723(12)  2831(11) 5281(9) 145(7)                                     C.sub.3g                                                                              6503(15)  3272(11) 6146(11)                                                                              204(8)                                     C.sub.4g                                                                              5037(14)  3498(11) 5737(10)                                                                              170(8)                                     O.sub.1h                                                                              2342(7)   4602(4)  3279(6) 97(3)                                      C.sub.1h                                                                              1316(11)  5151(7)  2894(10)                                                                              112(5)                                     C.sub.2h                                                                              2017(16)  5830(9)  2541(11)                                                                              153(7)                                     C.sub.3h                                                                              3180(12)  5561(10) 2425(10)                                                                              131(6)                                     C.sub.4h                                                                              3551(13)  4848(7)  3070(11)                                                                              115(6)                                     O.sub.1i                                                                              1391(7)   1752(4)  -1377(4)                                                                              80(2)                                      C.sub.1i                                                                              2235(19)  1594(11) -1998(13)                                                                             160(8)                                     C.sub.2i                                                                              2716(17)  2287(14) -2337(15)                                                                             165(10)                                    C.sub.3i                                                                              1991(28)  2906(11) -1934(14)                                                                             204(12)                                    C.sub.4i                                                                              1010(16)  2533(7)  -1523(9)                                                                              128(6)                                     O.sub.1j                                                                              3037(5)   155(4)   -264(5) 72(2)                                      C.sub.1j                                                                              4389(10)  48(7)    427(9)  113(5)                                     C.sub.2j                                                                              4998(16)  -571(10) -23(16) 174(8)                                     C.sub.3j                                                                              4001(11)  -840(8)  -1006(10)                                                                             127(6)                                     C.sub.4j                                                                              2778(11)  -493(7)  -974(8) 92(4)                                      ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i    the last significant digit.                                                    .sup.b Atoms are labeled in agreement with Figures 5 and 6.                   .sup.c This is onethird of the trace of the orthogonalized B.sub.1j           tensor.                                                                  

                                      TABLE XII                                   __________________________________________________________________________    Anisotropic Thermal Parameters for                                            Nonhydrogen Atoms in crystalline                                              4(OC.sub.4 H.sub.8)[Cr(NC.sub.4 H.sub.4).sub.5 (OC.sub.4 H.sub.8)[Na].sub.    Atom                                                                              Anisotropic Thermal Parameter (Å.sup.2 × 10)                    Type.sup.c                                                                        B.sub.11                                                                           B.sub.22                                                                           B.sub.33                                                                           B.sub.12                                                                            B.sub.13                                                                           B.sub.23                                        __________________________________________________________________________    Anion                                                                         Cr  29(1)                                                                              31(1)                                                                              38(1)                                                                              1(1)  12(1)                                                                              1(1)                                            N.sub.1a                                                                          33(2)                                                                              44(3)                                                                              44(3)                                                                              -1(2) 11(2)                                                                              5(2)                                            C.sub.1a                                                                          48(4)                                                                              37(3)                                                                              59(4)                                                                              -0(3) 15(3)                                                                              3(3)                                            C.sub.2a                                                                          55(4)                                                                              61(5)                                                                              90(5)                                                                              -19(4)                                                                              34(4)                                                                              13(4)                                           C.sub.3a                                                                          37(3)                                                                              82(6)                                                                              76(5)                                                                              -9(3) 33(3)                                                                              2(4)                                            C.sub.4a                                                                          40(3)                                                                              64(5)                                                                              52(4)                                                                              4(3)  16(3)                                                                              -5(3)                                           N.sub.1b                                                                          36(2)                                                                              44(3)                                                                              36(3)                                                                              7(2)   5(2)                                                                              12(2)                                           C.sub.1b                                                                          52(4)                                                                              51(4)                                                                              40(3)                                                                              -1(3)  9(3)                                                                              10(3)                                           C.sub.2b                                                                          73(5)                                                                              85(6)                                                                              83(6)                                                                              2(5)  13(4)                                                                              44(5)                                           C.sub.3b                                                                          51(4)                                                                              88(6)                                                                              54(4)                                                                              0(4)  -13(3)                                                                             12(4)                                           C.sub.4b                                                                          41(3)                                                                              55(4)                                                                              45(3)                                                                              0(3)   5(2)                                                                              4(4)                                            N.sub.1c                                                                          33(2)                                                                              41(3)                                                                              39(3)                                                                              4(2)   9(2)                                                                              1(2)                                            C.sub.1c                                                                          52(4)                                                                              51(4)                                                                              51(4)                                                                              6(3)  16(3)                                                                              5(3)                                            C.sub.2c                                                                          64(5)                                                                              62(5)                                                                              37(4)                                                                              -1(4) -4(3)                                                                              4(4)                                            C.sub.3c                                                                          32(3)                                                                              92(6)                                                                              89(6)                                                                              4(4)  -3(4)                                                                              29(5)                                           C.sub.4c                                                                          42(3)                                                                              78(5)                                                                              48(4)                                                                              -1(3)  9(3)                                                                              14(4)                                           N.sub.1d                                                                          31(2)                                                                              44(3)                                                                              56(3)                                                                              4(2)  13(2)                                                                              -1(3)                                           C.sub.1d                                                                          44(3)                                                                              60(5)                                                                              39(4)                                                                              -5(3)  8(3)                                                                              -11(3)                                          C.sub.2d                                                                          63(4)                                                                              70(6)                                                                              84(6)                                                                              -11(4)                                                                              20(4)                                                                              -47(5)                                          C.sub.3d                                                                          69(4)                                                                              43(4)                                                                              73(5)                                                                              9(3)  32(4)                                                                              -14(4)                                          C.sub.4d                                                                          42(3)                                                                              53(4)                                                                              63(4)                                                                              8(3)  17(3)                                                                              3(4)                                            N.sub.1e                                                                          47(3)                                                                              36(3)                                                                              39(3)                                                                              -3(2) 17(2)                                                                              -7(2)                                           C.sub.1e                                                                          59(4)                                                                              49(4)                                                                              53(4)                                                                              -15(3)                                                                              11(3)                                                                              -1(4)                                           C.sub.2e                                                                          92(5)                                                                              48(4)                                                                              69(5)                                                                              -20(4)                                                                              36(4)                                                                              -26(4)                                          C.sub.3e                                                                          91(6)                                                                              45(5)                                                                              106(7)                                                                             4(4)  37(5)                                                                              -13(5)                                          C.sub.4e                                                                          62(4)                                                                              23(3)                                                                              69(5)                                                                              7(3)  20(4)                                                                              -7(3)                                           O.sub.1f                                                                          40(2)                                                                              42(2)                                                                              51(2)                                                                              -4(2) 20(2)                                                                              2(2)                                            C.sub.1f                                                                          61(4)                                                                              64(5)                                                                              60(4)                                                                              -2(3) 39(3)                                                                              4(4)                                            C.sub.2f                                                                          81(6)                                                                              95(7)                                                                              144(8)                                                                             -24(5)                                                                              74(6)                                                                              1(6)                                            C.sub.3f                                                                          109(7)                                                                             80(6)                                                                              117(7)                                                                             -26(5)                                                                              75(6)                                                                              -3(6)                                           C.sub.4f                                                                          61(4)                                                                              53(4)                                                                              85(5)                                                                              -27(4)                                                                              30(4)                                                                              -16(4)                                          Cation 1                                                                      Na.sub.1                                                                          57(2)                                                                              71(2)                                                                              95(2)                                                                              -13(1)                                                                              21(2)                                                                              -2(2)                                           Cation 2                                                                      Na.sub.2                                                                          68(2)                                                                              69(2)                                                                              56(2)                                                                              -2(1) 30(1)                                                                              -3(2)                                           Solvent Molecules of Crystallization                                          O.sub.1g                                                                          58(3)                                                                              95(4)                                                                              92(4)                                                                              -8(3) 15(3)                                                                              -2(4)                                           C.sub.1g                                                                          54(5)                                                                              215(14)                                                                            108(8)                                                                             0(7)  29(5)                                                                              -7(9)                                           C.sub.2g                                                                          96(7)                                                                              226(15)                                                                            121(9)                                                                             52(9) 43(7)                                                                              51(10)                                          C.sub.3g                                                                          129(10)                                                                            277(19)                                                                            148(11)                                                                            52(12)                                                                              -56(9)                                                                             -134(13)                                        C.sub.4g                                                                          134(10)                                                                            250(18)                                                                            128(10)                                                                            44(11)                                                                              39(9)                                                                              -89(11)                                         O.sub.1h                                                                          71(4)                                                                              68(4)                                                                              152(6)                                                                             -8(3) 32(4)                                                                              -3(4)                                           C.sub.1h                                                                          92(7)                                                                              95(8)                                                                              144(9)                                                                             -2(6) 28(7)                                                                              -3(7)                                           C.sub.2h                                                                          212(14)                                                                            108(9)                                                                             140(10)                                                                            36(10)                                                                               50(10)                                                                            66(9)                                           C.sub.3h                                                                          99(8)                                                                              175(14)                                                                            101(8)                                                                             -6(9) -2(6)                                                                              32(9)                                           C.sub.4h                                                                          99(8)                                                                              79(7)                                                                              168(11)                                                                            -13(6)                                                                              38(8)                                                                              29(8)                                           O.sub.1i                                                                          98(4)                                                                              82(4)                                                                              73(3)                                                                              8(3)  47(3)                                                                              13(3)                                           C.sub.1i                                                                          230(15)                                                                            128(11)                                                                            168(12)                                                                             8(11)                                                                              131(12)                                                                            74(10)                                          C.sub.2i                                                                          112(10)                                                                            222(21)                                                                            156(15)                                                                             1(12)                                                                               28(10)                                                                            23(16)                                          C.sub.3i                                                                          370(26)                                                                            124(12)                                                                            135(12)                                                                            -93(15)                                                                              99(15)                                                                            34(10)                                          C.sub.4i                                                                          223(13)                                                                            81(7)                                                                              106(8)                                                                             32(8) 91(9)                                                                              31(6)                                           O.sub.1j                                                                          59(3)                                                                              64(3)                                                                              94(4)                                                                              5(3)  22(3)                                                                              -21(3)                                          C.sub.1j                                                                          88(7)                                                                              101(8)                                                                             133(9)                                                                             19(6)  2(6)                                                                              -58(7)                                          C.sub.2j                                                                          94(8)                                                                              190(14)                                                                            205(13)                                                                            73(10)                                                                              -11(9)                                                                             -90(13)                                         C.sub.3j                                                                          83(7)                                                                              130(10)                                                                            160(10)                                                                            16(7) 20(7)                                                                              -86(9)                                          C.sub.4j                                                                          82(6)                                                                              104(8)                                                                             92(7)                                                                              -7(6) 29(5)                                                                              -41(6)                                          __________________________________________________________________________     .sup.a The numbers in parentheses are the estimated standard deviations i    the last significant digit.                                                    .sup.b The form of the anisotropic thermal parameter is given in referenc    8 on page 6 of the structure report.                                           .sup.c Atoms are labeled in agrement with Figures 5 and 6.               

                  TABLE XIII                                                      ______________________________________                                        Atomic coordinates for Hydrogen Atoms in Crystalline                          [Cr(NC.sub.4 H.sub.4).sub.5 (OC.sub.4 H.sub.8)](Na).sub.2 --4(OC.sub.4        H.sub.8)                                                                      Atom        Fractional Coordinates                                            Type.sup.b                                                                             10.sup.4 x 10.sup.4 y 10.sup.4 z                                     ______________________________________                                                      Anion                                                           H.sub.1a 1061       3165       1756                                           H.sub.2a 3182       3406       1151                                           H.sub.3a 4547       2153       1428                                           H.sub.4a 3162       1162       2059                                           H.sub.1b 637        254        4479                                           H.sub.2b 2692       174        6022                                           H.sub.3b 4453       1179       5753                                           H.sub.4b 3373       1775       4016                                           H.sub.1c -326       2281       132                                            H.sub.2c -2637      2453       -1199                                          H.sub.3c -4426      2031       -243                                           H.sub.4c -3137      1655       1623                                           H.sub.1d 1070       2197       4997                                           H.sub.2d 349        3499       5480                                           H.sub.3d -1115      4135       3762                                           H.sub.4d -1278      3184       2317                                           H.sub.1e -1346      578        293                                            H.sub.2e -630       -712       -243                                           H.sub.3e 1503       -1135      1285                                           H.sub.4e 1999       -107       2676                                           H.sub.1fa                                                                              -1447      1250       4520                                           H.sub.1fb                                                                              -2339      1762       3588                                           H.sub.2fa                                                                              -4069      899        3170                                           H.sub.2fb                                                                              -3468      674        4380                                           H.sub.3fa                                                                              -2341      -312       4022                                           H.sub.3fb                                                                              -3620      -314       2996                                           H.sub.4fa                                                                              -2417      184        1980                                           H.sub.4fb                                                                              -1165      -201       2831                                                         Solvent of Crystallization                                      H.sub.1ga                                                                              6103       3536       4135                                           H.sub.1gb                                                                              5503       2694       3909                                           H.sub.2ga                                                                              6629       2283       5371                                           H.sub.2gb                                                                              7629       2940       5209                                           H.sub.3ga                                                                              6644       2947       6766                                           H.sub.3gb                                                                              7102       3717       6322                                           H.sub.4ga                                                                              4960       4045       5839                                           H.sub.4gb                                                                              4493       3223       6118                                           H.sub.1ha                                                                              596        4950       2301                                           H.sub.1hb                                                                              921        5310       3451                                           H.sub.2ha                                                                              2205       6231       3073                                           H.sub.2hb                                                                              1449       6034       1874                                           H.sub.3ha                                                                              3066       5447       1684                                           H.sub.3hb                                                                              3908       5936       2669                                           H.sub.4ha                                                                              4260       4953       3725                                           H.sub.4hb                                                                              3874       4459       2671                                           H.sub.1ia                                                                              3007       1289       -1594                                          H.sub.1ib                                                                              1721       1306       -2615                                          H.sub.2ia                                                                              3703       2328       -2031                                          H.sub.2ib                                                                              2496       2303       -3103                                          H.sub.3ia                                                                              1541       3249       -2509                                          H.sub.3ib                                                                              2638       3195       -1381                                          H.sub.4ia                                                                              101        2580       -2020                                          H.sub.4ib                                                                              1010       2761       -851                                           H.sub.1ja                                                                              4929       513        470                                            H.sub.1jb                                                                              4341       -91        1129                                           H.sub.2ja                                                                              5823       -388       -178                                           H.sub.2jb                                                                              5232       -992       479                                            H.sub.3ja                                                                              3930       -1396      -1018                                          H.sub.3jb                                                                              4261       -668       -1623                                          H.sub.4ja                                                                              2185       -862       -715                                           H.sub.4jb                                                                              2215       -324       -1678                                          ______________________________________                                         .sup.a Hydrogen atoms were included in the structure factor calculations      as idealized atoms (assuming sp.sup.2 or sp.sup.3hybridization of the         carbon atoms and a C--H bond length of 0.96Å) "riding" on their           respective carbon atoms. The isotropic thermal parameter of each hydrogen     atom was fixed at 1.2 times the equivalent isotropic thermal parameter of     the carbon atom to which it is covalently bonded.                             .sup.b Hydrogen atoms are labeled with the same numerical and literal         subscripts as their carbon atoms with an additional literal subscript (a,     or b) where necessary to distinguish between hydrogen atoms bonded to the     same carbon.                                                             

                  TABLE XIV                                                       ______________________________________                                        Bond Lengths Involving Nonhydrogen Atoms in                                   Crystalline [CR(NC.sub.4 H.sub.4).sub.5 (OC.sub.4 H.sub.8)[Na].sub.2          --4(OC.sub.4 H.sub.8)                                                         Type.sup.b                                                                              Length, Å                                                                             Type.sup.b                                                                              Length, Å                                 ______________________________________                                        Cr--N.sub.1a                                                                             2.035(6)   Na.sub.1 --O.sub.1g                                                                      2.314(6)                                     Cr--N.sub.1b                                                                             2.056(5)   Na.sub.1 --O.sub.1h                                                                      2.271(8)                                     Cr--N.sub.1c                                                                             2.044(5)                                                           Cr--N.sub.1d                                                                             2.114(6)   Na.sub.2 --O.sub.1i                                                                      2.365(7)                                     Cr--N.sub.1e                                                                             2.024(6)   Na.sub.2 --O.sub.1j                                                                      2.307(7)                                     Cr--O.sub.1f                                                                             2.120(5)   C.sub.1g --C.sub.2g                                                                     1.33(2)                                                 .           C.sub.2g --C.sub.3g                                                                     1.43(2)                                       N.sub.1a --C.sub.1a                                                                     1.36(1)     C.sub.3g --C.sub.4g                                                                     1.47(2)                                       N.sub.1a --C.sub.4a                                                                     1.38(1)     C.sub.1h --C.sub.2h                                                                     1.51(2)                                       N.sub.1b --C.sub.1b                                                                     1.33(1)     C.sub.2h --C.sub.3h                                                                     1.30(2)                                       N.sub.1b --C.sub.4b                                                                     1.37(1)     C.sub.3h --C.sub.4h                                                                     1.48(2)                                       N.sub.1c --C.sub.1c                                                                     1.41(1)     C.sub.1i --C.sub.2i                                                                     1.41(3)                                       N.sub.1c --C.sub.4c                                                                     1.35(1)     C.sub.2i --C.sub.3i                                                                     1.47(3)                                       N.sub.1d --C.sub.1d                                                                     1.34(1)     C.sub.3i --C.sub.4i                                                                     1.40(3)                                       N.sub.1d -- C.sub.4d                                                                    1.36(1)     C.sub.1j --C.sub.2j                                                                     1.44(2)                                       N.sub.1e --C.sub.1e                                                                     1.40(1)     C.sub.2j --C.sub.3j                                                                     1.46(2)                                       N.sub.1e --C.sub.4e                                                                     1.39(1)     C.sub.3j --C.sub.4j                                                                     1.42(2)                                       O.sub.1f --C.sub.1f                                                                     1.42(1)     O.sub.1g --C.sub.1g                                                                     1.38(1)                                       O.sub.1f --C.sub.4f                                                                     1.44(1)     O.sub.1g --C.sub.4g                                                                     1.32(1)                                                             O.sub.1h --C.sub.1h                                                                     1.38(1)                                       C.sub.1a --C.sub.2a                                                                     1.39(1)     O.sub.1h --C.sub.4h                                                                     1.39(2)                                       C.sub.2a --C.sub.3a                                                                     1.38(1)     O.sub.1i --C.sub.1i                                                                     1.36(2)                                       C.sub.3a --C.sub.4a                                                                     1.37(1)     O.sub.1i --C.sub.4i                                                                     1.40(1)                                       C.sub.1b --C.sub.2b                                                                     1.33(1)     O.sub.1j --C.sub.1j                                                                     1.41(1)                                       C.sub.2b --C.sub.3b                                                                     1.42(1)     O.sub.1j --C.sub.4j                                                                     1.43(1)                                       C.sub.3b --C.sub.4b                                                                     1.31(1)                                                             C.sub.1c --C.sub.2c                                                                     1.37(1)     Na.sub.1 --C.sub.1a                                                                      2.678(8)                                     C.sub.2c --C.sub.3c                                                                     1.41(1)     Na.sub.1 --N.sub.1d                                                                      2.688(7)                                     C.sub.3c --C.sub.4c                                                                     1.39(1)     Na.sub.1 --C.sub.1d                                                                      2.2621(9)                                    C.sub.1d --C.sub.2d                                                                     1.37(1)                                                             C.sub.2d --C.sub.3d                                                                     1.40(1)                                                             C.sub.3d --C.sub.4d                                                                     1.34(1)     Na.sub.2 --C.sub.4a                                                                      2.681(7)                                     C.sub.1e --C.sub.2e                                                                     1.37(1)     Na.sub.2 -- C.sub.1e                                                                     2.630(9)                                     C.sub.2e --C.sub.3e                                                                     1.43(1)                                                             C.sub.3e --C.sub.4e                                                                     1.37(1)                                                             C.sub.1f --C.sub.2f                                                                     1.50(1)                                                             C.sub.2f --C.sub.3f                                                                     1.43(2)                                                             C.sub.3f --C.sub.4f                                                                     1.49(2)                                                             ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i    the last significant digit.                                                    .sup.b Atoms are labeled in agreement with FIG. 6.                       

                  TABLE XV                                                        ______________________________________                                        Bond Angles Involving Nonhydrogen Atoms in                                    [Cr(NC.sub.4 H.sub.4).sub.3 (OC.sub.4 H.sub.8)[Na].sub.2 --4(OC.sub.4         H.sub.8)                                                                      Type.sup.b                                                                              Angle, deg  Type.sup.b                                                                              Angle, deg                                    ______________________________________                                        N.sub.1a CrN.sub.1b                                                                     91.2(2)     O.sub.1g Na.sub.1 O.sub.1h                                                              92.3(3)                                       N.sub.1a CrN.sub.1c                                                                     91.4(2)     O.sub.1g Na.sub.1 C.sub.1a                                                              114.3(3)                                      N.sub.1a CrN.sub.1d                                                                     91.1(2)     O.sub.1g Na.sub.1 N.sub.1d                                                              139.6(3)                                      N.sub.1a CrN.sub.1e                                                                     92.8(2)     O.sub.1g Na.sub.1 C.sub.1d                                                              118.0(3)                                      N.sub.1a CrO.sub.1f                                                                     178.7(2)    O.sub.1h Na.sub.1 C.sub.1a                                                              95.6(3)                                       N.sub.1b CrN.sub.1c                                                                     176.2(2)    O.sub.1h Na.sub.1 N.sub.1d                                                              127.0(2)                                      N.sub.1b CrN.sub.1d                                                                     86.7(2)     O.sub.1b Na.sub.1 C.sub.1d                                                              132.1(3)                                      N.sub.1b CrN.sub.1e                                                                     93.3(2)     C.sub.1a Na.sub.1 N.sub.1d                                                              75.1(2)                                       N.sub.1b CrO.sub.1f                                                                     88.5(2)     C.sub.1a Na.sub.1 C.sub.1d                                                              103.1(3)                                      N.sub.1c CrN.sub.1d                                                                     90.4(2)     N.sub.1d Na.sub.1 C.sub.1d                                                              29.3(2)                                       N.sub.1c CrN.sub.1e                                                                     89.4(2)                                                             N.sub.1c CrO.sub.1f                                                                     88.8(2)     O.sub.1i Na.sub.2 O.sub.1j                                                              90.7(3)                                       N.sub.1d CrN.sub.1e                                                                     176.1(2)    O.sub.1i Na.sub.2 C.sub.4a                                                              109.3(3)                                      N.sub.1d CrO.sub.1f                                                                     87.6(2)     O.sub.1i Na.sub.2 C.sub.1e                                                              131.5(2)                                      N.sub.1e CrO.sub.1f                                                                     88.5(2)     O.sub.1j Na.sub.2 C.sub.4a                                                              103.2(2)                                                            O.sub.1j Na.sub.2 C.sub.1e                                                              115.1(3)                                      CrN.sub.1a C.sub.1a                                                                     124.7(5)    C.sub.4a Na.sub.2 C.sub.1e                                                              103.9(3)                                      CrN.sub.1a C.sub.4a                                                                     126.3(5)                                                            CrN.sub.1b C.sub.1b                                                                     127.0(4)    Na.sub.1 O.sub.1g C.sub.1g                                                              131.4(6)                                      CrN.sub.1b C.sub.4b                                                                     127.3(5)    Na.sub.1 O.sub.1g C.sub.4g                                                              124.0(8)                                      CrN.sub.1c C.sub.1c                                                                     128.5(5)    Na.sub.1 O.sub.1h C.sub.1h                                                              132.2(7)                                      CrN.sub.1c C.sub.4c                                                                     126.7(5)    Na.sub.1 O.sub.1h C.sub.4h                                                              116.6(6)                                      CrN.sub.1d C.sub.1d                                                                     127.7(5)    Na.sub.2 O.sub.1i C.sub.1i                                                              120.9(8)                                      CrN.sub.1d C.sub.4d                                                                     125.7(5)    Na.sub.2 O.sub.1i C.sub.4i                                                              126.8(7)                                      CrN.sub.1e C.sub.1e                                                                     127.7(5)    Na.sub.2 O.sub.1j C.sub.1j                                                              123.1(6)                                      CrN.sub.1e C.sub.4e                                                                     126.2(4)    Na.sub.2 O.sub.1j C.sub.4j                                                              125.8(5)                                      CrO.sub.1f C.sub.1f                                                                     126.4(4)    C.sub.1g O.sub.1g C.sub.4g                                                              104.3(8)                                      CrO.sub.1f C.sub.4f                                                                     123.1(5)    C.sub.1h O.sub.1h C.sub.4h                                                              108.9(9)                                                            C.sub.1i O.sub.1i C.sub.4i                                                              107.8(11)                                     C.sub.1a N.sub.1a C.sub.4a                                                              105.9(6)    C.sub.1j O.sub.1j C.sub.4j                                                              107.7(7)                                      C.sub.1b N.sub.1b C.sub.4b                                                              105.2(5)                                                            C.sub.1c N.sub.1c C.sub.4c                                                              104.0(5)    O.sub.1g C.sub.1g C.sub.2g                                                              111(1)                                        C.sub.1d N.sub.1d C.sub.4d                                                              106.6(6)    C.sub.1g C.sub.2g C.sub.3g                                                              103(1)                                        C.sub.1e N.sub.1e C.sub.4e                                                              106.6(6)    C.sub.2g C.sub.3g C.sub.4g                                                              103(1)                                                              C.sub.3g C.sub.4g O.sub.1g                                                              110(1)                                        C.sub.1f O.sub.1f C.sub.4f                                                              110.5(6)    O.sub.1h C.sub.1h C.sub.2h                                                              106(1)                                                              C.sub.1h C.sub.2h C.sub.3h                                                              106(1)                                        N.sub.1a C.sub.1a C.sub.2a                                                              111.1(7)    C.sub.2h C.sub.3h C.sub.4h                                                              109(1)                                        C.sub.1a C.sub.2a C.sub.3a                                                              106.1(8)    C.sub.3h C.sub.4h O.sub.1h                                                              106(1)                                        C.sub.2a C.sub.3a C.sub.4a                                                              107.5(7)    O.sub.1i C.sub.1i C.sub.2i                                                              110(2)                                        C.sub.3a C.sub.4a N.sub.1a                                                              110.3(7)    C.sub.1i C.sub.2i C.sub.3i                                                              105(2)                                        N.sub.1b C.sub.1b C.sub.2b                                                              110.6(7)    C.sub.2i C.sub.3i C.sub.4i                                                              106(2)                                        C.sub.1b C.sub.2b C.sub.3b                                                              107.6(8)    C.sub.3i C.sub.4i O.sub.1i                                                              107(1)                                        C.sub.2b C.sub.3b C.sub.4b                                                              104.4(7)    O.sub.1j C.sub.1j C.sub.2j                                                              106(1)                                        C.sub.3b C.sub.4b N.sub.1b                                                              112.2(7)    C.sub.1j C.sub.2j C.sub.3j                                                              109(1)                                        N.sub.1c C.sub.1c C.sub.2c                                                              112.4(7)    C.sub.2j C.sub.3j C.sub.4j                                                              104(1)                                        C.sub.1c C.sub.2c C.sub.3c                                                              104.5(7)    C.sub.3j C.sub.4j O.sub.1j                                                              108(1)                                        C.sub.2c C.sub.3c C.sub.4c                                                              107.8(7)                                                            C.sub.3c C.sub.4c N.sub.1c                                                              111.2(7)    Na.sub.1 C.sub.1a N.sub.1a                                                              95.0(4)                                       N.sub.1d C.sub.1d C.sub.2d                                                              109.0(7)    Na.sub.1 C.sub.1a C.sub.2a                                                              106.7(5)                                      C.sub.1d C.sub.2d C.sub.3d                                                              107.6(8)    Na.sub.1 N.sub.1d Cr                                                                    107.7(3)                                      C.sub.2d C.sub.3d C.sub.4d                                                              105.4(8)    Na.sub.1 N.sub.1d C.sub.1d                                                              72.6(4)                                       C.sub.3d C.sub.4d N.sub.1d                                                              111.5(7)    Na.sub.1 N.sub.1d C.sub.4d                                                              86.4(4)                                       N.sub.1e C.sub.1e C.sub.2e                                                              111.0(7)    Na.sub.1 C.sub.1d N.sub.1d                                                              78.1(4)                                       C.sub.1e C.sub.2e C.sub.3e                                                              105.2(7)    Na.sub.1 C.sub.1d C.sub.2d                                                              85.1(6)                                       C.sub.2e C.sub.3e C.sub.4e                                                              108.4(8)                                                            C.sub.3e C.sub.4e N.sub.1e                                                              109.5(7)    Na.sub.2 C.sub.4a N.sub.1a                                                              90.2(3)                                                             Na.sub.2 C.sub.4a C.sub.3a                                                              104.0(5)                                      C.sub.1f C.sub.1f C.sub.2f                                                              104.4(7)    Na.sub.2 C.sub.1e N.sub.1e                                                              78.1(4)                                       C.sub.1f C.sub.2f C.sub.3f                                                              105.0(9)    Na.sub.2 C.sub.1e C.sub.2e                                                              91.7(6)                                       C.sub.2f C.sub.3f C.sub.4f                                                              104.9(9)                                                            C.sub.3f C.sub.4f O.sub.1f                                                              104.7(7)                                                            ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i    the last significant digit.                                                    .sup.b Atoms are labeled in agreement with FIG. 6.                       

EXAMPLE VII

The product obtained from the reaction of sodium 2,5-dimethylpyrrolideand CrCl₂ used in the preparation of an active catalyst was a light bluesolid, Product VI. 2,5-Dimethylpyrrole (5.0 ml/49.1 mmole) was mixedwith excess sodium (40% dispersion in mineral spirits) intetrahydrofuran (125 ml) at ambient temperature. The mixture wasrefluxed 12 hours under nitrogen then filtered to remove excess sodium.The sodium 2,5-dimethylpyrrolide was used in-site and combined withchromous chloride(3.03 g/24.7 mmole) at ambient temperature. Thereaction mixture was refluxed under nitrogen for 48 hours. Thegray-green solution was filtered(medium porosity frit) at ambienttemperature and stripped of solvent undervacuum, then pumped dry undervacuum for 12 hours resulting in a gray/greensolid. This gray/greensolid was then washed with pentane resulting in a light blue solid,Product VI, which was collected by filtration. Product VI was used inthe preparation of an active catalyst without further purification.

EXAMPLE VIII Preparation of Catalysts

All polymerization runs were carried out in a two liter reactor underslurry (particle form) conditions. The diluent was isobutane and thereactor temperature was 90° C. Reactor pressure held at 550 psig duringthe polymerization, with ethylene being fed on demand.

The actual charging of the reactor was accomplished by the followingmethod. After purging the reactor at 100° C. with a stream of nitrogenfor at least 15 minutes, the reactor temperature was lowered to 90° C.and a preweighed amount of supported chromium pyrrolide catalyst wascharged against a slight countercurrent of nitrogen. One liter ofisobutane was then charge to the reactor and finally the reactorpressurized with ethylene.

The ethylene consumed was determined using a precalibrated ethylene flowmeter. Samples of the liquid product mixture were taken after 30 minuterun time without depressurizing the reactor. This was done by filling to200-300 psig a steel sampling cylinder adapted to the reactor with a diptube fitted with a fritted tip extending into the bottom of the reactorvessel. Samples taken this way were analyzed by gas chromatography andgaschromatography-mass spectrometry. Selectivities were normalized to100%. Solid products were obtained by venting the reactor to atmosphere,separating by decantation of the liquids from the solid material. Thesolids were then dried at 100° C. in a vacuum oven and weighed. Theyieldof solid product was obtained by weighing the combined solid andcatalyst residues and subtracting from this the preweighed catalystcharge. The yield of volatile products was obtained by subtracting theyield of solid products from the grams of ethylene consumed as recordedbythe flow meter.

Activity typically ranged from 300-1500 g product/g catalyst/hourcalculated for 30 minute run time, as shown in Table XVI. The productobtained typically was represented by 97-99.5% by weight liquids and0.5-3% by weight polymer (wax). The liquid fraction was typically 85%hexanes, 11% decenes, 2% tetradecences, based on the total weight of theliquid fraction. The balance of the liquid product mixture was a tracelevel distribution of olefins typically totaling about 1-2% by weight ofthe product mixture, see Table XVII.

Active catalysts were prepared from the chromium pyrrolide complexes asfollows. All toluene and/or pentane rinses used about 15 to about 30 mlsof liquid.

Run 1: 0.158 g of Product V (prepared in THF solvent), which was heatedto 80° C. for 4 hours under nitrogen flush to remove residual THF,wasslurried with 15 ml toluene at ambient temperature. 9.0 ml of a 1MTEA in hexanes solution was added to the solution and stirred for 24hours. The formation of a brown solution and the complete dissolution ofProduct V resulted immediately upon TEA addition. AlPO₄ (P/Al moleratio=0.4) (2.00 g) was added to the solution and stirred for anadditional 24 hours.The supported catalyst was filtered from thesolution as a brown solid, rinsed twice with toluene, and then twicewith pentane. 0.3143 g of the catalyst was charged directly to thereactor for polymerization. 1.0 ml ofa 0.5% TEA in heptanes solution wascharged to the reactor after the catalyst charge but before theisobutane (reactor solvent) charge to purgefeedstock poisons.

Run 2: 0.081 g of Product V (prepared in THF solvent), which was heatedto 80° C. for 4 hours under nitrogen flush to remove residual THF,wasslurried with 15 ml diethylbenzene at ambient temperature. 2.0 ml ofa 1M TEA in hexanes solution was added to the solution and stirred for24 hours. The formation of a brown solution and the complete dissolutionof Product V resulted immediately upon TEA addition. AlPO₄ (P/Al moleratio=0.4) (1.50 g) was added to the solution and stirred for anadditional 1 hour. The supported catalyst was filtered from the solutionas a brown solid, rinsed twice with dimethylbenzene, and then twice withpentane. 0.4333 g of the catalyst was charged directly to the reactorfor polymerization. 3.0 ml of a 0.5% TEA in heptanes solution wascharged to the reactor after the catalyst charge but before theisobutane (reactor solvent) charge to purge feedstock poisons.

Run 3: 0.093 g of Product V (prepared in DME solvent) was slurried with15 ml toluene at ambient temperature. 5.0 ml of a 1M TEA in hexanessolution was added to the solution and stirred for 24 hours. Theformation of a brown solution and the complete dissolution of Product Vresulted immediately upon TEA addition. AlPO₄ (P/Al mole ratio=0.4) (1.0g) was added to the solution and stirred for an additional 24 hours. Thesupported catalyst was filtered from the solution as a brown solid,rinsedtwice with toluene, and then twice with pentane. 0.1564 g of thecatalyst was charged directly to the reactor for polymerization. 3.0 mlof a 0.5% TEA in heptanes solution was charged to the reactor after thecatalyst charge but before the isobutane (reactor solvent) charge topurge feedstock poisons.

Run 4: 0.080 g of Product I (prepared in THF solvent) was slurried with15 ml toluene at ambient temperature. 6.0 ml of a 1M TEA in hexanessolution was added and the solution stirred for 16 hours. The formationof a brown solution and the complete dissolution of Product I resultedimmediately upon TEA addition. AlPO₄ (P/Al mole ratio=0.4) (1.50 g) wasadded to the solution and stirred for an additional 16 hours. Thesupported catalyst was filtered from the solution as a brown solid,rinsed twice with toluene, and then twice pentane. 1.1988 g of thecatalyst was chargeddirectly to the reactor for polymerization.

Run 5: 0.079 g of Product II (prepared in THF solvent) was slurried with15ml toluene at ambient temperature. 2.0 ml of a 1.9M TEA in toluenesolutionwas added to the solution and stirred for 8 hours. The formationof a brownsolution and the complete dissolution of Product II resultedimmediately upon TEA addition. AlPO₄ (P/Al mole ratio=0.4) (0.50 g) wasadded to the solution and stirred for an additional 16 hours. Thesupported catalyst was filtered from the solution as a brown solid,rinsed twice with toluene, and then twice with pentane. 0.4829 g of thecatalyst was charged directly to the reactor for polymerization.

Run 6: 0.071 g of Product V (prepared in THF solvent), which was heatedto 80° C. for 4 hours under nitrogen flush to remove residual THF,wasslurried with 15 ml toluene at ambient temperature. 2.0 ml of a 1MTEA in hexanes solution was added to the solution and stirred for 1hour. The formation of a brown solution and the complete dissolution ofProduct V resulted immediately upon TEA addition. SiO₂ (2.52 g) wasadded to the solution and stirred for an additional 2 minutes. Thesupported catalyst was filtered from the solution as a brown solid,rinsed twice with toluene, and then twice with pentane. All of thecatalyst was chargeddirectly to the reactor for polymerization.

Run 7: 0.103 g of Product II (prepared in THF solvent) was slurried with15ml toluene at ambient temperature. 1.0 ml of a 1.9M TEA in toluenesolutionwas added to the solution and stirred for 10 minutes. Theformation of a brown solution and the complete dissolution of Product IIresulted immediately upon TEA addition. Al₂ O₃ (2.27 g) was added to thesolution and stirred for an additional 2 minutes. The supported catalystwas filtered from the solution as a brown solid, rinsed twice withtoluene, and then twice with pentane. 1.2926 g of the catalyst waschargeddirectly to the reactor for polymerization.

Run 8: 0.120 g of Product I (prepared in THF solvent) was slurried with15 ml toluene at ambient temperature. 2.0 ml of a 1M TEA in hexanessolution was added to the solution and stirred for 2 days. The formationof a brownsolution and the complete dissolution of Product I resultedimmediately upon TEA addition. SiO₂ (1.0 g) was added to the solutionand stirredfor an additional 3 weeks. The supported catalyst wasfiltered from the solution as a brown solid, rinsed twice with toluene,and then twice with pentane. All of the catalyst was charged directly tothe reactor for polymerization.

Run 9: 0.106 g of Product III (prepared in THF solvent) was slurriedwith 15 ml toluene at ambient temperature. 2.5 ml of a 1.9M TEA intoluene solution was added to the solution and stirred for 2 hours. Theformation of a brown solution and the complete dissolution of ProductIII resulted immediately upon TEA addition. AlPO₄ (P/Al mole ratio=0.4)(0.65 g) was added to the solution and stirred for an additional 2hours. The supported catalyst was filtered from the solution as a brownsolid, rinsedtwice with toluene, and then twice with pentane. All of thecatalyst was charged directly to the reactor for polymerization. 1.5 mlof a 1.0% TEA in pentane solution was charged to the reactor after thecatalyst charge but before the isobutane (reactor solvent) charge topurge feedstock poisons.

Run 10: 0.030 g of Product V (prepared in THF solvent) which was heatedto 80° C. for 4 hours under nitrogen flush to remove residual THF wasslurried with 15 ml toluene at ambient temperature. 3.0 ml of a 1M TEAin hexanes solution was added to the solution and stirred for 16 hours.The formation of a brown solution and the complete dissolution ofProduct V resulted immediately upon TEA addition. AlPO₄ (P/Al=0.9) (2.0g) was added to the solution and stirred for an additional 16 hours. Thesupported catalyst was filtered from the solution as a brown solid,rinsedtwice with toluene, and then twice with pentane. 0.322/g ofcatalyst was charged directly to the reactor for polymerization.

Run 11: 0.067 g of Product V (prepared in THF solvent) was slurried with15ml pentane at ambient temperature. 4.0 ml of a 1M TEA in hexanessolution was added to the solution and stirred for 24 hours. Theformation of a brown solution and the complete dissolution of Product Vresulted immediately upon TEA addition. AlPO₄ (P/Al mole ratio=0.4) (1.0g) was added to the solution and stirred for an additional 24 hours. Thesupported catalyst was filtered from the solution as a brown solid,rinsedtwice with pentane. All of the catalyst was charged directly tothe reactorfor polymerization. 3.0 ml of a 0.5% TEA in heptanes solutionwas charged to the reactor after the catalyst charge but before theisobutane (reactorsolvent) charge to purge feedstock poisons.

Run 12: 0.073 g of Product V (prepared in THP solvent), which was heatedto80° C. for 4 hours under nitrogen flush to remove residual THF, wasslurried with 15 ml toluene at ambient temperature. 6.0 ml of a 1M TEAin hexanes solution was added and the solution stirred for 24 hours. Theformation of a brown solution and the complete dissolution of Product Vresulted immediately upon TEA addition. P/SiO₂ (7.0 g) was added to thesolution and stirred for an additional 24 hours which nearly decolorizedit. The supported catalyst was filtered from the solution as abrownsolid, rinsed twice with toluene, and then twice with pentane. 2.85 gofcatalyst was charged directly to the reactor for polymerization.

Run 13: 0.125 g or Product II was slurried with 15 ml diethylbenzene atambient temperature. 9.0 ml of a 1M TEA in hexanes solution was added tothe solution and stirred for 8 hours. The formation of a brown solutionand the complete dissolution of Product II resulted immediately upon TEAaddition. F/Al₂ O₃ (2.0 g) was added to the solution and stirredfor anadditional 12 hours. The supported catalyst was filtered from thesolution as a brown solid, rinsed twice with toluene, and then twicewith pentane. 0.5477 g of catalyst was charged directly to the reactorfor polymerization.

Run 14: 0.125 g of Product VI was slurried with 15 ml toluene at ambienttemperature. 1.5 ml of a 1M TEA in hexanes solution was added and thesolution stirred for 10 minutes. The formation of a red/brown solutionandthe complete dissolution of Product VI resulted immediately upon TEAaddition. SiO₂ (2.0 g) was added to the solution and stirred for anadditional 1 minute which nearly decolorized it. The supported silicacatalyst was filtered from the solution as a red/brown solid, rinsedtwicewith toluene, and then twice with pentane. All of the catalyst wascharged directly to the reactor for polymerization.

Run 15: 0.30 g of Product V (prepared in DME solvent) was dissolved with15ml of dimethoxyethane forming a green solution. This solution was thenmixed with 0.6 g of AlPO₄ (P/Al₄ mole ratio=0.4) (2.00 g) and themixture was stirred 1 hour. The green supported material was filteredfrom the solution, rinsed with dimethoxyethane and dried with a nitrogenpurge at 90° C. This material was then stirred with 15 ml of toluene and3 ml of triethylaluminum (Aldrich 1.0M, hexanes) for an additional 3hours. The brown supported catalyst was collected by filtration, rinsedwith pentane, and dried under vacuum. 0.4609 g of the catalyst wascharged directly to the reactor for polymerization. 3.0 ml ofa 0.5% TEAin heptanes solution was charged to the reactor after the catalystcharge but before the isobutane (reactor solvent) charge topurgefeedstock poisons.

Run 16: 0.058 g of Product V (prepared in THF solvent) which was heatedto 80° C. for 4 hours under nitrogen flush to remove residual THF wasslurried with 15 ml benzene at ambient temperature. 4.0 ml of a 1H TEAin hexanes solution was added and the solution stirred for 2 hours. Theformation of a brown solution and the complete dissolution of Product Vresulted immediately upon TEA addition. AlPO₄ (P/Al mole ratio=0.4) (1.0g) was added to the solution and stirred for 1 hour. The supportedcatalyst was filtered from the solution as a brown solid, rinsed twicewith benzene, and then twice with pentane. All of the catalyst waschargeddirectly to the reactor for polymerization. 3.0 ml of a 0.5% TEAin heptanes solution was charged to the reactor after the catalystcharge butbefore the isobutane (reactor solvent) charge to purgefeedstock poisons.

Run 17: 0.1610 g of Product T was charged directly to the reactor at 90°C. The reactor was charged with 1 liter isobutane and pressurized to 550psig with ethylene. No ethylene consumption was detected, therefore 50psig of dihydrogen was charged to the reactor whichdid not initiateethylene consumption. Ethylene consumption was initiated after 2.0 ml of1M TEA in hexanes solution was charged.

Run 18: 0.3528 g of Product VI was charged directly to the reactor at90° C. The reactor was charged with 1 liter isobutane and pressurized to550 psig with ethylene. No ethylene consumption was detected, therefore2.0 ml of a 1M TEA in hexanes solution was charged which did initiateethylene consumption.

Run 19: 0.3482 g of Product VI was charged directly to the reactor at90° C. The reactor was also charged with 2.0 ml of a 1M TEA in hexanessolution prior to a 1 liter isobutane charge. The reactor wasthenpressurized to 550 psig with ethylene. No ethylene consumption wasdetected, therefore 30 psi of dihydrogen was charged to the reactorwhich initiated ethylene consumption.

Run 20: 0.202 g of Product V (prepared in dimethoxyethane (DME)solvent), 6.0 ml of a 1.9M TEA in toluene solution, and 2.0 g of AlPO₄(P/Al mole ratio=0.4) were mixed with 15 ml toluene at ambienttemperature. The formation of a brown solution and the completedissolution of Product V resulted immediately upon mixing. The brownsolution was stirred for 48 hours. The supported catalyst was filteredfrom the solution as a brown solid, rinsed twice with toluene, and thentwice with pentane. 0.0671 g ofthe catalyst was charged directly to thereactor for polymerization. 1.0 mlof a 0.5% TEA in heptanes solution wascharged to the reactor after the catalyst charge but before theisobutane (reactor solvent) charge to purgefeedstock poisons.

The data in Table XVI show that the inventive chromium compounds can beused either supported (Runs 1-16, 20) or unsupported (Runs 17-19) topolymerize and/or trimerize olefins. Furthermore, conditions can bevariedto increase the amount of trimer product (Runs 1-5 and 9) or tohave a higher yield of solid, or polymer, product (Runs 6, 7, and 13).Runs 1, 3,and 20 demonstrate that high activities are attainable.

                                      TABLE XVI                                   __________________________________________________________________________    Run.sup.a                                                                        Catalyst     Support.sup.b                                                                        Products      Activity.sup.c                           __________________________________________________________________________     1 (V)/TEA/Toluene                                                                            AlPO.sub.4                                                                           98.4% liquids, 1.6% solids                                                                  1030                                      2 (V)/TEA/Diethylbenzene                                                                     AlPO.sub.4                                                                           99.4% liquids, 0.6% solids                                                                  730                                       3 (V)/TEA/Toluene                                                                            AlPO.sub.4                                                                           99.4% liquids, 0.6% solids                                                                  1450                                      4 (I)/TEA/Toluene                                                                            AlPO.sub.4                                                                           98.6% liquids, 1.4% solids                                                                  .sup. 360.sup.d                           5 (II)/TEA/Toluene                                                                           AlPO.sub.4                                                                           98.2% liquids, 1.8% solids                                                                  580                                       6 (V)/TEA/Toluene                                                                            SiO.sub.2                                                                            89.0% liquids, 11.0% solids                                                                  80                                       7 (II)/TEA/Toluene                                                                           Al.sub.2 O.sub.3                                                                     55.8% liquids, 44.2% solids                                                                  50                                       8 (I)/TEA/Toluene                                                                            SiO.sub.2                                                                            93.3% liquids, 6.7% solids                                                                  400                                       9 (III)/TEA/Toluene                                                                          AlPO.sub.4                                                                           99.8% liquids, 0.2% solids                                                                  100                                      10 (V)/TEA/Toluene                                                                            AlPO.sub.4 (.9)                                                                      96.8% liquids, 3.2% solids                                                                  930                                      11 (V)/TEA/Pentane                                                                            AlPO.sub.4                                                                           (trace) liquids, (trace) solids                                                             unreactive                               12 (V)/TEA/Toluene                                                                            P/SiO.sub.2                                                                          98.1% liquids, 1.9% solids                                                                   90                                      13 (II)/TEA/Diethylbenzene                                                                    F/Al.sub.2 O.sub.3                                                                   88.0% liquids, 12.0% solids                                                                 300                                      14 (VI)/TEA/Toluene                                                                           SiO.sub.2                                                                            94.3% liquids, 5.7% solids                                                                   40                                      15 (V)/DME      AlPO.sub.4                                                                           90.8% liquids, 2.0% solids                                                                  550                                      16 (V)/TEA/Benzene                                                                            AlPO.sub.4                                                                           99.1% liquids, 0.9% solids                                                                  500                                      17 (I)/TEA      unsupported                                                                          98.3% liquids, 1.7% solids                                                                  340                                      18 (VI)/TEA     unsupported                                                                          99.4% liquids, 0.6% solids                                                                  180                                      19 (VI)/TEA     unsupported                                                                          98.1% liquids, 1.9% solids                                                                  230                                      20 (V)/TEA      AlPO.sub.4                                                                           99.5% liquids, 0.5% solids                                                                  2760                                     __________________________________________________________________________     .sup.a All runs made at 90° C., isobutane solvent, 550 psi total       pressure.                                                                     .sup.b P/Al mole ratio = 0.4; except Run 10 whereby P/Al mole ratio = 0.9     .sup.c Grams product/grams catalyst/hour based on 30 min. run times.          .sup.d Believed to be lower than actual due to experimental error; actual     value believe to be near 2000.                                           

                  TABLE XVII                                                      ______________________________________                                                                                       C16--                          Run  C4     1-hexene C6    C8   C10  C12  C14  C28                            ______________________________________                                        1    0.05   81.92    7.76  0.49 9.12 0.09 0.52 .05                            2    0.10   78.80    7.49  0.58 11.36                                                                              0.10 1.01 .56                            3    0.06   82.19    7.68  0.45 8.85 0.08 0.58 .11                            5    0.10   83.40    7.08  0.62 8.08 0.05 0.42 .25                            6    0.55   78.70    5.52  1.84 11.24                                                                              0.42 1.26 .47                            16   0.06   72.85    13.61 0.31 12.06                                                                              0.09 0.93 .09                            19   6.03   71.66    6.09  3.61 9.42 1.17 1.41 .61                            ______________________________________                                    

EXAMPLE IX

Single crystal x-ray structures were obtained for Cr(NC₄ H₄)₃ Cl(O₂ C₂H₄ (CH₃)₂)₃ Na, shown in FIGS. 7 and 8, and Cr(NC₄ H₄)₃ Cl(O₂ C₂ H₄(CH₃)₂), and shown in FIG. 9. These crystals were obtained in accordancewith the procedure given in Example III. However, x-ray quality crystalswere obtained after the dark green, filtered solution was maintained atambient temperature and pressure under an inertatmosphere, nitrogen, fora time of about 2 days. Analysis calculated for C₂₄ H₄₂ N₃ O₆ CrNaCl: C,49-78; H, 7.31; N, 7.26% by weight. Found: C, 49.80; H 7.39; N, 7.18% byweight.

The description of the single-crystal sample and mounting used for datacollection are as follows:

Color: Green/black

Shape: Rectangular parallelepiped

Dimensions: 0.44×0.62×0.62 mm

Crystal Mount: Crystal was glued to the inside of a thin-walled glasscapillary and sealed under N₂.

Crystal Orientation: Crystal was oriented with its longer edges nearlyparallel to the phi axis of the diffractometer.

Width at Half-height from ω Scans: 0.38°

The space group and cell data are as follows:

Crystal System: Monoclinic

Space Group and Number:² P2₁ /c-C_(2h) ⁵ (No. 14)

Number of Computer-Centered Reflections Used in the Least-SquaresRefinement of the Cell Dimensions: ##EQU4##Lattice Constants with esd's:

    ______________________________________                                        a = 8.135(2)Å                                                                           α = 90.00°                                                                    V = 3027(1)Å                                   b = 22.337(5)Å                                                                          β = 91.67(2)°                                                                  Z = 4                                              c = 16.667(4)Å                                                                          Γ = 90.00°                                                                    λ = 0.71073Å                            ______________________________________                                    

Molecular Weight: 579.05 amu

Calculated Density: 1.271 g/cn⁻³

Linear Absorption Coefficient:^(3a) 0.51 mm⁻¹

Tables XVIII-XXII list the resultant parameters used to generate themolecular structures shown in FIGS. 7 and 8.

                  TABLE XVIII                                                     ______________________________________                                        Atomic Coordinates for Nonhydrogen Atoms in                                   Crystalline [Cr(NC.sub.4 H.sub.4).sub.3 (Cl)(O.sub.2 C.sub.2 H.sub.4          (CH.sub.3).sub.2).sub.3 Na].sup.a                                                                       Equivalent Isotropic                                Atom   Fractional Coordinates                                                                           Thermal Parameter,                                  Type.sup.b                                                                           10.sup.4 x                                                                             10.sup.4 y                                                                              10.sup.4 z                                                                          B, Å.sup.2 × 10.sup.c               ______________________________________                                        Cr     -1030(1) 559(1)    3005(1)                                                                             30(1)                                         Cl     135(1)   -26(1)    1981(1)                                                                             41(1)                                         Na     -2167(2) -1011(1)  1832(1)                                                                             46(1)                                         N.sub.1                                                                              -3062(4) 65(2)     2907(2)                                                                             35(1)                                         C.sub.11                                                                             -4107(5) 63(2)     2251(3)                                                                             40(1)                                         C.sub.12                                                                             -5189(5) -409(2)   2291(3)                                                                             51(1)                                         C.sub.13                                                                             -4810(5) -713(2)   2998(3)                                                                             51(1)                                         C.sub.14                                                                             -3512(5) -414(2)   3361(3)                                                                             46(1)                                         N.sub.2                                                                              -1817(4) 1027(2)   3950(2)                                                                             37(1)                                         C.sub.21                                                                             -1188(6) 1558(2)   4234(3)                                                                             47(1)                                         C.sub.22                                                                             -2205(7) 1790(2)   4799(3)                                                                             60(2)                                         C.sub.23                                                                             -3499(7) 1398(2)   4874(3)                                                                             60(2)                                         C.sub.24                                                                             -3248(5) 934(2)    4349(2)                                                                             43(1)                                         N.sub.3                                                                              -1892(4) 1185(2)   2260(2)                                                                             35(1)                                         C.sub.31                                                                             -3100(5) 1588(2)   2434(3)                                                                             41(1)                                         C.sub.32                                                                             -3573(6) 1901(2)   1757(3)                                                                             53(1)                                         C.sub.33                                                                             -2631(6) 1686(2)   1130(3)                                                                             51(1)                                         C.sub.34                                                                             -1620(6) 1249(2)   1453(3)                                                                             46(1)                                         O.sub.1a                                                                             1317(3)  971(1)    3154(2)                                                                             40(1)                                         O.sub.2a                                                                             153(3)   -12(1)    3878(2)                                                                             40(1)                                         C.sub.1a                                                                             2459(5)  631(2)    3651(3)                                                                             53(1)                                         C.sub.2a                                                                             1443(6)  329(2)    4268(3)                                                                             53(1)                                         C.sub.3a                                                                             2156(6)  1247(2)   2495(3)                                                                             58(2)                                         C.sub.4a                                                                             653(6)   -625(2)   3733(3)                                                                             49(1)                                         O.sub.1b                                                                             -2558(4) -783(2)   398(2)                                                                              62(1)                                         O.sub.2b                                                                             -3877(5) -1772(2)  111(2)                                                                              76(1)                                         C.sub.1b                                                                             -3618(9) -1166(3)  -25(4)                                                                              89(2)                                         C.sub.2b                                                                             -3627(9) -1765(3)  302(4)                                                                              83(2)                                         C.sub.3b                                                                             -2410(8) -207(3)   61(4) 79(2)                                         C.sub.4b                                                                             -4149(9) -2328(3)  1440(5)                                                                             106(3)                                        O.sub.1c                                                                             -1334(4) -1823(2)  2911(2)                                                                             65(1)                                         O.sub.2c                                                                             235(5)   -1589(2)  1529(3)                                                                             87(2)                                         C.sub.1c                                                                             71(7)    -2144(3)  2724(4)                                                                             83(2)                                         C.sub.2c                                                                             951(8)   -1913(4)  2067(4)                                                                             107(3)                                        C.sub.3c                                                                             -2090(8) -2017(3)  3614(4)                                                                             83(2)                                         C.sub.4c                                                                             1224(8)  -1393(3)  900(4)                                                                              88(2)                                         ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i    the last significant digit.                                                    .sup.b Atoms are labeled in agreement with FIG. 7.                            .sup.c This is onethird of the trace of the orthogonalized B.sub.ij           tensor.                                                                  

                  TABLE XIX                                                       ______________________________________                                        Anisotropic Thermal Parameters for Nonhydrogen Atoms                          in Crystalline [Cr(NC.sub.4 H.sub.4).sub.3 (Cl)(O.sub.2 C.sub.2 H.sub.4       (CH.sub.3).sub.2).sub.3 Na]                                                   Atom  Anisotropic Thermal Parameter (Å.sup.2 × 10)                  Type.sup.c                                                                          B.sub.11 B.sub.22                                                                              B.sub.33                                                                             B.sub.12                                                                            B.sub.13                                                                             B.sub.23                           ______________________________________                                        Cr    28(1)    31(1)   30(1)  2(1)  -0(1)  -2(1)                              Cl    39(1)    43(1)   41(1)  2(1)  5(1)   -9(1)                              Na    47(1)    48(1)   44(1)  0(1)  3(1)   -4(1)                              N.sub.1                                                                             37(1)    39(2)   35(2)  0(1)  2(1)   -3(1)                              C.sub.11                                                                            31(2)    47(2)   41(2)  0(2)  -1(2)  -7(2)                              C.sub.12                                                                            33(2)    59(3)   61(3)  -3(2) -4(2)  -16(2)                             C.sub.13                                                                            35(2)    39(2)   79(3)  -6(2) 8(2)   3(2)                               C.sub.14                                                                            39(2)    45(2)   54(2)  1(2)  2(2)   10(2)                              N.sub.2                                                                             36(2)    38(2)   36(2)  7(1)  -3(1)  -8(1)                              C.sub.21                                                                            55(2)    38(2)   47(2)  9(2)  -6(2)  -5(2)                              C.sub.22                                                                            88(3)    46(3)   44(2)  32(2) -9(2)  -12(2)                             C.sub.23                                                                            65(3)    74(3)   42(2)  32(2) 7(2)   0(2)                               C.sub.24                                                                            37(2)    55(2)   37(2)  14(2) -0(2)  1(2)                               N.sub.3                                                                             38(2)    35(2)   32(2)  3(1)  0(1)   -0(1)                              C.sub.31                                                                            35(2)    43(2)   43(2)  6(2)  -(2)   1(2)                               C.sub.32                                                                            52(2)    47(2)   58(3)  8(2)  -11(2) 6(2)                               C.sub.33                                                                            62(3)    51(3)   39(2)  -2(2) -8(2)  12(2)                              C.sub.34                                                                            52(2)    45(2)   40(2)  -1(2) 2(2)   2(2)                               O.sub.1a                                                                            32(1)    40(1)   50(2)  -1(1) -3(1)  -5(1)                              O.sub.2a                                                                            40(1)    38(1)   41(1)  6(1)  -7(1)  -1(1)                              C.sub.1a                                                                            33(2)    50(3)   73(3)  4(2)  -13(2) -10(2)                             C.sub.2a                                                                            53(2)    55(3)   51(2)  10(2) -24(2) -10(2)                             C.sub.3a                                                                            45(2)    53(3)   76(3)  -15(2)                                                                              8(2)   -5(3)                              C.sub.4a                                                                            50(2)    40(2)   58(3)  12(2) -8(2)  -1(2)                              O.sub.1b                                                                            76(2)    63(2)   47(2)  -14(2)                                                                              -5(2)  1(2)                               O.sub.2b                                                                            101(3)   62(2)   63(2)  -28(2)                                                                              -5(2)  -2(2)                              C.sub.1b                                                                            120(5)   91(4)   56(3)  -29(4)                                                                              -25(3) -3(3)                              C.sub.2b                                                                            116(5)   64(3)   68(4)  -18(3)                                                                              -24(3) -12(3)                             C.sub.3b                                                                            81(4)    84(4)   72(4)  -9(3) -1(3)  19(3)                              C.sub.4b                                                                            118(5)   84(4)   113(5) -51(4)                                                                              -38(4) 29(4)                              O.sub.1c                                                                            61(2)    64(2)   70(2)  8(2)  0(2)   4(2)                               O.sub.2c                                                                            74(2)    76(3)   112(3) 29(2) 31(2)  30(2)                              C.sub.1c                                                                            73(3)    65(3)   113(5) 23(3) 9(3)   25(3)                              C.sub.2c                                                                            83(4)    146(6)  96(5)  61(4) 24(4)  14(5)                              C.sub.3c                                                                            84(4)    64(3)   101(5) -8(3) 3(4)   16(3)                              C.sub.4c                                                                            77(4)    98(5)   90(5)  13(3) 29(3)  -5(4)                              ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i    the last significant digit.                                                    .sup.b The form of the anisotropic thermal parameter is given in referenc    8 on page 6 of the crystal structure analysis report.                          .sup.c Atoms are labeled in agreement with FIG. 7.                       

                  TABLE XX                                                        ______________________________________                                        Atomic Coordinates for Hydrogen Atoms in Crystalline                          [Cr(NC.sub.4 H.sub.4).sub.3 (Cl)(O.sub.2 C.sub.2 H.sub.4 (CH.sub.3).sub.2)    .sub.3 Na]                                                                    Atom        Fractional Coordinates                                            Type.sup.b                                                                             10.sup.4 x 10.sup.4 y 10.sup.4 z                                     ______________________________________                                        H.sub.11 -4089      350        1823                                           H.sub.12 -6043      -509       1905                                           H.sub.13 -5349      -1064      3195                                           H.sub.14 -2993      -526       3863                                           H.sub.21 -188       1740       4063                                           H.sub.22 -2044      2158       5089                                           H.sub.23 -4404      1441       5226                                           H.sub.24 -3967      597        4273                                           H.sub.31 -3554      1644       2954                                           H.sub.32 -4392      2210       1720                                           H.sub.33 -2680      1817       581                                            H.sub.34 -840       1021       1159                                           H.sub.1aa                                                                              3014       339        3336                                           H.sub.1ab                                                                              3254       892        3906                                           H.sub.2aa                                                                              967        626        4606                                           H.sub.2ab                                                                              2127       67         4588                                           H.sub.3aa                                                                              1391       1487       2185                                           H.sub.3ab                                                                              2589       938        2162                                           H.sub.3ac                                                                              3040       1495       2696                                           H.sub.4aa                                                                              -256       -834       3484                                           H.sub.4ab                                                                              926        -806       4242                                           H.sub.4ac                                                                              1586       -646       3395                                           H.sub.1ba                                                                              -4712      -1006      -11                                            H.sub.1bb                                                                              -3277      -1186      -570                                           H.sub.2ba                                                                              -2588      -1951      204                                            H.sub.2bb                                                                              -4492      -1988      37                                             H.sub.3ba                                                                              -1696      26         407                                            H.sub.3bb                                                                              -3461      -14        7                                              H.sub.3bc                                                                              -1935      -243       -458                                           H.sub.4ba                                                                              -4380      -2289      2000                                           H.sub.4bb                                                                              -3108      -2524      1385                                           H.sub.4bc                                                                              -4998      -2561      1178                                           H.sub.1ca                                                                              795        -2146      3189                                           H.sub.1cb                                                                              -255       -2547      2596                                           H.sub.2ca                                                                              1398       -2252      1795                                           H.sub.2cb                                                                              1831       -1676      2294                                           H.sub.3ca                                                                              -3168      -1848      3661                                           H.sub.3cb                                                                              -1397      -1884      4055                                           H.sub.3cc                                                                              -2164      -2446      3624                                           H.sub.4ca                                                                              456        -1357      454                                            H.sub.4cb                                                                              2033       -1690      780                                            H.sub.4cc                                                                              1756       -1015      996                                            ______________________________________                                         .sup.a The 6 methyl groups were refined as rigid rotors with                  sp.sup.3hybridized geometry and C--H bond lengths of 0.96Å. The           initial orientation of each methyl group was determined from difference       Fourier positions for the hydrogen atoms. The final orientation of each       methyl group was determined by three rotational parameters. The refined       positions for the rigid rotor methyl groups gave O--C--H angles which         ranged fro 103° to 115°. The remaining hydrogen atoms were      included in the structure factor calculations as idealized atoms (assumin    sp.sup.2 or sp.sup.3hybridization of the carbon atoms and a C--H bond          length of 0.96Å) "riding" on their respective carbon atoms. The           isotropic thermal parameter of each hydrogen was fixed at 1.2 times the       equivalent isotropic thermal parameter of the carbon atom to which it is      covalently bonded.                                                            .sup.b Hydrogens are labeled with the same subscripts as their carbon         atoms with an additional literal subscript (a, b or c) where necessary to     distinguish between hydrogen atoms bonded to the same carbon.            

                  TABLE XXI                                                       ______________________________________                                        Bond Lengths Involving Nonhydrogen Atoms in                                   Crystalline [Cr(NC.sub.4 H.sub.4).sub.3 (Cl)(O.sub.2 C.sub.2 H.sub.4          (CH.sub.3).sub.2).sub.3 Na].sup.a                                             Type.sup.b                                                                             Length, Å                                                                              Type.sup.b                                                                             Length, Å                                  ______________________________________                                        Cr--Cl   2.369(1)     Cr--N.sub.1                                                                            1.990(3)                                                             Cr--N.sub.2                                                                            2.010(3)                                       Cr--O.sub.1a                                                                           2.128(3)     Cr--N.sub.3                                                                            1.986(3)                                       Cr--O.sub.2a                                                                           2.142(3)                                                             N.sub.1 --C.sub.11                                                                     1.365(5)     C.sub.11 --C.sub.12                                                                    1.376(6)                                       N.sub.1 --C.sub.14                                                                     1.366(6)     C.sub.12 --C.sub.13                                                                    1.386(7)                                       N.sub.2 --C.sub.21                                                                     1.370(6)     C.sub.13 --C.sub.14                                                                    1.376(6)                                       N.sub.2 --C.sub.24                                                                     1.374(5)     C.sub.21 --C.sub.22                                                                    1.373(7)                                       N.sub.3 --C.sub.31                                                                     1.370(5)     C.sub.22 --C.sub.23                                                                    1.377(8)                                       N.sub.3 --C.sub.34                                                                     1.376(6)     C.sub.23 --C.sub.24                                                                    1.375(7)                                                             C.sub.31 --C.sub.32                                                                    1.373(7)                                       O.sub.1a --C.sub.1a                                                                    1.443(5)     C.sub.32 --C.sub.33                                                                    1.399(7)                                       O.sub.1a --C.sub.3a                                                                    1.448(6)     C.sub.33 --C.sub.34                                                                    1.375(7)                                       O.sub.2a --C.sub.2a                                                                    1.437(5)                                                             O.sub.2a --C.sub.4a                                                                    1.450(5)     C.sub.1a --C.sub.2a                                                                    1.498(7)                                       O.sub.1b --C.sub.1b                                                                    1.391(8)     C.sub.1b --C.sub.2b                                                                    1.445(9)                                       O.sub.1b --C.sub.3b                                                                    1.410(7)     C.sub.1c --C.sub.2c                                                                     1.422(10)                                     O.sub.2b --C.sub.2b                                                                    1.370(7)                                                             O.sub.2b --C.sub.4b                                                                    1.379(8)     Na . . . Cr                                                                            4.108(2)                                       O.sub.1c --C.sub.1c                                                                    1.392(7)                                                             O.sub.1c --C.sub.3c                                                                    1.408(8)     Na--Cl   2.896(2)                                       O.sub.2c --C.sub.2c                                                                    1.278(9)                                                             O.sub.2c --C.sub.4c                                                                    1.409(8)     Na--N.sub.1                                                                            3.098(4)                                       Na--C.sub.11                                                                           2.967(5)     Na--O.sub.1b                                                                           2.454(4)                                       Na--C.sub.12                                                                           2.924(5)     Na--O.sub.2b                                                                           2.483(4)                                       Na--C.sub.13                                                                           3.015(5)     Na--O.sub.1c                                                                           2.629(5)                                       Na--C.sub.14                                                                           3.104(5)     Na--O.sub.2c                                                                           2.408(5)                                       Na--C.sub.g1.sup.c                                                                      2.788(-)                                                            ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i    the last significant digit.                                                    .sup.b Atoms are labeled in agreement with FIG. 7.                            .sup.c The symbol C.sub.g1 is used to designate the center of gravity for     the fivemembered ring containing N.sub.1, C.sub.11, C.sub.12, C.sub.13,       and C.sub.14 ; this value is therefore listed without an estimated            standard deviation.                                                      

                  TABLE XXII                                                      ______________________________________                                        Bond Angles Involving Nonhydrogen Atoms in                                    Crystalline [Cr(NC.sub.4 H.sub.4).sub.3 (Cl)(O.sub.2 C.sub.2 H.sub.4          (CH.sub.3).sub.2).sub.3 Na].sup.a                                             Type.sup.b                                                                              Angle, deg.  Type.sup.b                                                                              Angle, deg.                                  ______________________________________                                        ClCrN.sub.1                                                                             89.1(1)      ClCrN.sub.2                                                                             173.9(1)                                     N.sub.1 CrN.sub.2                                                                       94.0(1)      ClCrN.sub.3                                                                             94.5(1)                                      N.sub.1 CrN.sub.3                                                                       93.5(1)      N.sub.2 CrN.sub.3                                                                       90.5(1)                                      ClCrO.sub.1a                                                                            86.9(1)      N.sub.1 CrO.sub.1a                                                                      171.9(1)                                     N.sub.2 CrO.sub.1a                                                                      89.4(1)      N.sub.3 CrO.sub.1a                                                                      93.8(1)                                      ClCrO.sub.2a                                                                            88.9(1)      N.sub.1 CrO.sub.2a                                                                      94.7(1)                                      N.sub.2 CrO.sub.2a                                                                      85.7(1)      N.sub.3 CrO.sub.2a                                                                      171.2(1)                                     O.sub.1a CrO.sub.2a                                                                     78.2(1)                                                             CrN.sub.1 C.sub.11                                                                      124.4(3)     C.sub.11 N.sub.1 C.sub.14                                                               105.7(3)                                     CrN.sub.1 C.sub.14                                                                      128.6(3)     C.sub.21 N.sub.2 C.sub.24                                                               106.1(4)                                     CrB.sub.2 C.sub.21                                                                      126.6(3)     C.sub.31 N.sub.3 C.sub.34                                                               106.0(3)                                     CrN.sub.2 C.sub.24                                                                      126.5(3)                                                            CrN.sub.3 C.sub.31                                                                      125.0(3)     CrO.sub.1a C.sub.1a                                                                     113.5(2)                                     CrN.sub.3 C.sub.34                                                                      128.3(3)     CrO.sub.1a C.sub.3a                                                                     122.5(3)                                                            C.sub.1a O.sub.1a C.sub.3a                                                              110.5(3)                                     N.sub.1 C.sub.11 C.sub.12                                                               110.3(4)     CrO.sub.2a C.sub.2a                                                                     107.4(2)                                     C.sub.11 C.sub.12 C.sub.13                                                              106.9(4)     CrO.sub.2a C.sub.4a                                                                     124.9(3)                                     C.sub.12 C.sub.13 C.sub.14                                                              106.5(4)     C.sub.2a O.sub.2a C.sub.4a                                                              111.8(3)                                     N.sub.1 C.sub.14 C.sub.13                                                               110.6(4)     C.sub.1b O.sub.1b C.sub.3b                                                              114.7(4)                                     N.sub.2 C.sub.21 C.sub.22                                                               109.7(4)     C.sub.2b O.sub.2b C.sub.4b                                                              115.6(5)                                     C.sub.21 C.sub.22 C.sub.23                                                              107.4(4)     C.sub.1c O.sub.1c C.sub.3c                                                              114.2(5)                                     C.sub.22 C.sub.23 C.sub.24                                                              107.1(4)     C.sub.2c O.sub.2c C.sub.4c                                                              116.0(5)                                     N.sub.2 C.sub.24 C.sub.23                                                               109.7(4)                                                            N.sub.3 C.sub.31 C.sub.32                                                               110.3(4)     O.sub.1a C.sub.1a C.sub.2a                                                              105.8(3)                                     C.sub.31 C.sub.32 C.sub.33                                                              107.0(4)     O.sub.2a C.sub.2a C.sub.1a                                                              109.8(4)                                     C.sub.32 C.sub.33 C.sub.34                                                              106.6(4)     O.sub.1b C.sub.1b C.sub.2b                                                              112.8(5)                                     N.sub.3 C.sub.34 C.sub.33                                                               110.2(4)     O.sub.2b C.sub.2b C.sub.1b                                                              112.6(5)                                                            O.sub.1c C.sub.1c C.sub.2c                                                              114.9(6)                                     ClNaC.sub.g1.sup.c                                                                      83.6(-)      O.sub.2c C.sub.2c C.sub.1c                                                              121.1(6)                                     ClNaO.sub.1b                                                                            89.5(1)      C.sub.g1 NaO.sub.1b.sup.c                                                               111.1(-)                                     ClNaO.sub.2b                                                                            156.0(1)     C.sub.g1 NaO.sub.2b.sup.c                                                               110.2(-)                                     ClNaO.sub.1c                                                                            108.2(1)     C.sub.g1 NaO.sub.1c.sup.c                                                               99.4(-)                                      ClNaO.sub.2c                                                                            84.2(1)      C.sub.g1 NaO.sub. 2c.sup.c                                                              155.9(-)                                     ClNaN.sub.1                                                                             61.5(1)      O.sub.1b NaO.sub.2b                                                                     67.4(2)                                      ClNaC.sub.11                                                                            73.3(2)      O.sub.1b NaO.sub.1c                                                                     146.4(2)                                     ClNaC.sub.12                                                                            100.0(2)     O.sub.1b NaO.sub.2c                                                                     89.4(2)                                      ClNaC.sub.13                                                                            104.4(2)     O.sub.2b NaO.sub.1c                                                                     89.3(2)                                      ClNaC.sub.14                                                                            81.1(2)      O.sub.2b NaO.sub.2c                                                                     88.8(2)                                                             O.sub.1c NaO.sub.2c                                                                     65.1(2)                                      N.sub.1 NaC.sub.11                                                                      25.9(2)                                                             N.sub.1 NaC.sub.14                                                                      25.5(2)      N.sub.1 NaC.sub.12                                                                      43.8(2)                                      C.sub.11 NaC.sub.12                                                                     27.0(2)      N.sub.1 NaC.sub.13                                                                      43.2(2)                                      C.sub.12 NaC.sub.13                                                                     26.9(2)      C.sub.11 NaC.sub.13                                                                     43.5(2)                                      C.sub.13 NaC.sub.14                                                                     25.9(2)      C.sub.12 NaC.sub.14                                                                     42.9(2)                                                             C.sub.11 NaC.sub.14                                                                     41.9(2)                                      ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i    the last significant digit.                                                    .sup.b Atoms are labeled in agreement with FIG. 7.                            .sup.c The symbol C.sub.g1 is used to designate the center of gravity for     the fivemember ring containing N.sub.1, C.sub.11, C.sub.12, C.sub.13, and     C.sub.14 ; this value is therefore listed without an estimated standard       deviation.                                                               

While this invention has been described in detail for the purpose ofillustration, it is not to be construed as limited thereby but isintendedto cover all changes and modifications within the spirit andscope thereof.

That which is claimed is:
 1. A trimerization process comprisingcontacting at least one mono-1-olefin with a catalyst prepared by aprocess comprising forming a mixture of and refluxing:(a) a chromiumsalt; (b) a metal amide which is a pyrrolide; and (c) an electron pairdonor solvent which can affect a reaction between the chromium salt andmetal amide.
 2. A process according to claim 1 wherein saidmono-1-olefin has from about 2 to about 30 carbon atoms per molecule. 3.A process according to claim 1 wherein said mono-1-olefin is ethylene.4. A trimerization process comprising contacting at least onemono-1-olefin with an alkyl aluminum activating compound selected fromthe group consisting of metal alkyls and Lewis acids and a catalystprepared by a process comprising forming a mixture of and refluxing:(a)a chromium salt; (b) a metal amide, which is a pyrrolide; and (c) anelectron pair donor solvent which can affect a reaction between thechromium salt and metal amide.
 5. A process according to claim 4 whereinsaid activating compound is a trialkylaluminum compound.
 6. A processaccording to claim 5 wherein said trialkylaluminum compound istriethylaluminum.
 7. A process according to claim 6 wherein saidactivating compound and said catalyst are supported on an inorganicoxide support.
 8. A process according to claim 7 wherein said activatingcompound, said catalyst and said inorganic oxide support are combined inthe presence of an aromatic hydrocarbon.
 9. A process according to claim4 wherein said mono-1-olefin has from 2 to about 8 carbon atoms permolecule and said contacting occurs at a temperature within a range ofabout 60° to about 110° C.
 10. A process to trimerize olefins comprisingcontacting at least one mono-1-olefin with a composition comprising Cr₅(C₄ H₄ N)₁₀ (C₄ H₈ O)₄ supported on an inorganic oxide and an alkylaluminum activating compound selected from the group consisting of metalalkyls and Lewis acids.
 11. A process according to claim 10 wherein saidmono-1-olefin has from 2 to about 8 carbon atoms per molecule and saidcontacting occurs at a temperature within a range of about 60° to about110° C.
 12. A process according to claim 10 wherein said activatingcompound, Cr₅ (C₄ H₄ N)₁₀ (C₄ H₈ O)₄ and said inorganic oxide supportare combined in the presence of an aromatic hydrocarbon.
 13. A processto trimerize olefins comprising contacting at least one mono-1-olefinwith a composition comprising Cr(C₄ H₄ N)₄ Na₂.2(OC₄ H₈) supported on aninorganic oxide and an alkyl aluminum activating compound selected fromthe group consisting of metal alkyls and Lewis acids.
 14. A processaccording to claim 13 wherein said mono-1-olefin has from 2 to about 8carbon atoms per molecule and said contacting occurs at a temperaturewithin a range of about 60° to about 110° C.
 15. A process according toclaim 13 wherein said activating compound, Cr(C₄ H₄ N)₄ Na₂.2(OC₄ H₈)and said inorganic oxide support are combined in the presence of anaromatic hydrocarbon.
 16. A process to trimerize olefins comprisingcontacting at least one mono-1-olefin with a composition comprisingCr(C₄ H₄ N)₅ (OC₄ H₈)Na₂.4(OC₄ H₈) supported on an organic oxide and analkyl aluminum activating compound selected from the group consisting ofmetal alkyls and Lewis acids.
 17. A process according to claim 16wherein said mono-1-olefin has from 2 to about 8 carbon atoms permolecule and said contacting occurs at a temperature within a range ofabout 60° to about 110° C.
 18. A process according to claim 16 whereinsaid activating compound, Cr(C₄ H₄ N)₅ (OC₄ H₈)Na₂.4(OC₄ H₈) and saidinorganic oxide support are combined in the presence of an aromatichydrocarbon.
 19. A process to trimerize olefins comprising contacting atleast one mono-1-olefin with a catalyst system prepared according to aprocess comprising:(a) forming a mixture of a chromium salt, a metalamide which is a pyrrolide, and electron pair donor solvent which canaffect a reaction between the chromium salt and metal amide; (b)recovering a chromium-containing compound from the mixture of (a); (c)reacting the chromium-containing compound of (b) with an aromaticcompound and an alkyl aluminum activating compound selected from thegroup consisting of metal alkyls and Lewis acids to form a reactionproduct; (d) adding an inorganic oxide to the reaction product of (c);and (e) recovering a solid product.
 20. A process according to claim 19wherein said mono-1-olefin has from 2 to about 8 carbon atoms permolecule and said contacting occurs at a temperature within a range ofabout 60° to about 110° C.
 21. A process according to claim 19 whereinsaid activating compound, said catalyst system and said inorganic oxidesupport are combined in the presence of an aromatic hydrocarbon.
 22. Aprocess to trimerize olefins comprising contacting at least onemono-1-olefin with a catalyst system prepared according to a processcomprising:(a) forming a mixture of and refluxing a chromium salt, ametal amide which is a pyrrolide, and an electron pair donating solventwhich can affect a reaction between the chromium salt and metal amide;(b) adding an inorganic oxide to the mixture of (a) to form a slurry;(c) recovering a supported chromium-containing solid product; (d) addingan alkyl aluminum activating compound selected from the group consistingof metal alkyls and Lewis acids to the solid product of (c); and (e)recovering a solid product.
 23. A process according to claim 22 whereinsaid mono-1-olefin has from 2 to about 8 carbon atoms per molecule andsaid contacting occurs at a temperature within a range of about 60° toabout 110° C.
 24. A process according to claim 22 wherein saidactivating compound, said catalyst system and said inorganic oxidesupport are combined in the presence of an aromatic hydrocarbon.
 25. Aprocess to trimerize olefins comprising contacting at least onemono-1-olefin with a catalyst composition comprising Cr(NC₄ H₄)₃ Cl(O₂C₂ H₄ (CH₃)₂)₃ Na supported on an inorganic oxide and an alkyl aluminumactivating compound selected from the group consisting of metal alkylsand Lewis acids.
 26. A process according to claim 25 wherein saidmono-1-olefin has from 2 to about 8 carbon atoms per molecule and saidcontacting occurs at a temperature within a range of about 60° to about110° C.
 27. A process according to claim 23 wherein said activatingcompound, Cr(NC₄ H₄)₃ Cl(O₂ C₂ H₄ (CH₃)₂)₃ Na and said inorganic oxidesupport are combined in the presence of an aromatic hydrocarbon.
 28. Aprocess to trimerize olefins comprising contacting at least onemono-1-olefin with a catalyst system prepared according to a processcomprising:(a) forming a mixture of and refluxing a chromium salt, ametal amide which is a pyrrolide, and electron pair donor solvent whichcan affect a reaction between the chromium salt and metal amide; (b)recovering a chromium-containing compound from the mixture of (a); and(c) reacting the chromium-containing compound of (b) with an alkylaluminum compound activating compound selected from the group consistingof metal alkyls and Lewis acids to form a reaction product.
 29. Aprocess according to claim 28 wherein said mono-1-olefin has from 2 toabout 8 carbon atoms per molecule and said contacting occurs at atemperature within a range of about 60° to about 110° C.
 30. A processaccording to claim 28 wherein said activating compound, said catalystsystem and said inorganic oxide support are combined in the presence ofan aromatic hydrocarbon.